Chapter 1

Perturbation theory

c B. Zwiebach
It is often the case that the Hamiltonian of a system differs slightly from a Hamiltonian
that is well studied and completely understood. This is a situation where perturbation the-
ory can be useful. Perturbation theory allows us to make statements about the Hamiltonian
of the system using what we know about the well studied Hamiltonian.
The well studied Hamiltonian could be the that of the simple harmonic oscillator in one,
two, or three dimensions. In a diatomic molecule, for example, the potential that controls
the vibrations is not exactly quadratic; it has extra terms that make the vibrations slightly
anharmonic. In that situation the extra terms in the potential represent perturbations of the
Hamiltonian. The hydrogen atom Hamiltonian is also a well understood system. If we place
the atom inside a weak external magnetic field or electric field, the situation is described by
adding some small terms to the hydrogen Hamiltonian. Similarly, the interaction between
the magnetic moments of the proton and the electron can be incorporated by modifying the
original hydrogen atom Hamiltonian. The interaction between two neutral hydrogen atoms
at a distance, leading to the van der Waals force can be studied in perturbation theory by
thinking of the two atoms as electric dipoles.
The Hamiltonian of interest is written as the understood, original Hamiltonian H (0) ,
plus a perturbation δH:
H (0) + δH . (1.0.1)
Since H (0) is Hermitian and the sum must be a Hermitian Hamiltonian, the perturbation
operator δH must also be Hermitian. It is convenient to introduce a unit-free constant
λ ∈ [0, 1] and to consider, instead, a λ-dependent Hamiltonian H(λ) that takes the form

H(λ) = H (0) + λ δH . (1.0.2)

When λ = 1 we have the Hamiltonian of interest, but λ allows us to consider a family of

Hamiltonians that interpolate from H (0) , when λ is equal to zero, to the Hamiltonian of
interest for λ equal to one. In many cases perturbations can be turned on and off; think,

1
2 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

for example, of an atom in an external magnetic field that can be varied continuously. In
that case we can view λ as the parameter that allows us to turn on the perturbation by
letting λ 6= 0. The parameter λ is also useful in organizing the perturbation analysis, as we
will see below.
We spoke of a Hamiltonian that differs slightly from H (0) . In order to use perturbation
theory we need λδH to be a ‘small’ perturbation of the Hamiltonian H (0) . We will have to
deal with the meaning of small. At first sight we may imagine that small means that, viewed
as matrices, the largest entries in λδH are smaller than the largest entries in H (0) . While
this is necessary, more is needed, as we will see in our analysis. An additional advantage of
using λ is that by taking it to be sufficiently small we can surely make λδH small.
We assume that the Hamiltonian H (0) is understood, namely, we know the eigenstates
and eigenvalues of H (0) . We want to know the eigenstates and eigenvalues of H(λ). One may
be able to calculate those exactly, but this is seldom a realistic possibility. Diagonalizing δH
is seldom useful, since δH and H do not generally commute and therefore δH eigenstates are
not eigenstates of H(λ). In perturbation theory the key assumption is that the eigenvalues
and eigenvectors of H(λ) can be found as series expansions in powers of λ. We hope, of
course, that there are some values of λ for which the series converges, or at least gives useful
information.

Figure 1.1: The energy eigenvalues of H(λ) as λ varies from zero to one. On the λ = 0 vertical
axis the H (0) eigenstates are represented by heavy dots. By the time λ = 1 the dots have shifted.

In Figure 1.1 we illustrate some of the phenomena that we may see in the spectrum
of a system with Hamiltonian H(λ). We show how the energies of the various states may
change as the parameter λ is increased from zero. The two lowest energy eigenstates are
non-degenerate and their energies can go up and down as λ varies. Next up in energy we
have two degenerate states of H (0) (the Hamiltonian as λ = 0). The perturbation splits the
1.1. NONDEGENERATE PERTURBATION THEORY 3

two levels, and that happens generically. In the figure, the perturbation splits the levels to
first order in λ, as shown by the different slopes of the two curves that meet at λ = 0. In
other words, viewed as power series in λ the energies of the two states have different linear
terms in λ. The last level shown corresponds to four degenerate states. The perturbation
to first order in λ splits the states into a group of three states and a fourth. To second order
in λ the three states split further. A single Hamiltonian can exhibit behavior like this, with
many possible variations.
To analyze the evolution of states and energies as functions of λ we have two possible
cases: (i) we are following a non-degenerate state or, (ii) we are following a collection of
degenerate states. The challenges are quite different and therefore we must analyze them
separately. Clearly both situations can occur for a single Hamiltonian, depending on the
spectrum of H (0) . To follow a non-degenerate state we use non-degenerate perturbation
theory. To follow a set of degenerate states we use degenerate perturbation theory. Since
Hamiltonians H (0) generally have both non-degenerate and degenerate states we need to
consider both types of perturbation theory. We begin with non-degenerate perturbation
theory.

1.1 Nondegenerate perturbation theory

We begin by describing the original Hamiltonian H (0) . We assume this Hamiltonian has a
discrete spectrum with an orthonormal basis |k(0) i of energy eigenstates, where k ∈ Z is a
label that ranges over a possibly infinite set of values:
(0)
H (0) |k(0) i = Ek |k(0) i , hk(0) |l(0) i = δkl . (1.1.1)

We will let k = 0 denote the ground state and we order the states so that the energies
generally increase as the value of the label increases, so that
(0) (0) (0) (0)
E0 ≤ E1 ≤ E2 ≤ E3 ≤ ... (1.1.2)

The equal signs are needed because some states may be degenerate.
In this section we focus on a non-degenerate state |n(0) i with fixed n. This means that
|n(0) i is a single state that is separated by some finite energy from all the states with more
energy and from all the states with less energy. In other words the following must be part
of the sequence of inequalities in (1.1.2)
(0) (0)
. . . ≤ En−1 < En(0) < En+1 ≤ . . . (1.1.3)
(0) (0)
If the chosen state is the ground state, we have instead E0 < E1 .
As the perturbation is turned on by making λ different from zero, the energy eigenstate
|n(0) i of H (0) will evolve into some energy eigenstate |niλ of H(λ) with energy En (λ):

H(λ)|niλ = En (λ) |niλ , (1.1.4)

4 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

where
|niλ=0 = |n(0) i , and En (λ = 0) = En(0) . (1.1.5)
As we said, the solution is assumed to take the form of a regular power series expansion
in λ. To make this clear consider a function f (λ) such that its derivatives to all orders exist
for λ = 0. In that case we have a Taylor expansion
∞
X 1 (n)
f (λ) = f (0) λn = f (0) + f ′ (0) λ + 12 f ′′ (0) λ2 + 1 ′′′
3! f (0) λ
3
+ ··· (1.1.6)
n!
n=0

The expansion is a power series in λ, with coefficients f (0), f ′ (0), etc, that are λ independent
and reflect the value of the function and its derivatives at λ = 0.
For our problem we note the values of |niλ and En (λ) for λ = 0 (1.1.5) and write:

|niλ = |n(0) i + λ|n(1) i + λ2 |n(2) i + λ3 |n(3) i + . . . ,

(1.1.7)
En (λ) = En(0) + λ En(1) + λ2 En(2) + λ3 En(3) + . . .
The superscripts on the states and energies denote the power of λ that accompanies them
in the above expressions. The above equations are a natural assumption; they state that
the perturbed states and energies, being functions of λ, admit a Taylor expansion around
λ = 0. Our aim is to calculate the states

|n(1) i , |n(2) i , |n(3) i , . . . (1.1.8)

and the energies

En(1) , En(2) , En(3) , . . . (1.1.9)
Note that all these states and energies are, by definition, λ independent. Here |n(1) i is the
(1)
leading correction to the state |n(0) i as we turn on λ, and En is the leading correction to
the energy as we turn on λ. We will not impose the requirement that |niλ is normalized. It
suffices that |niλ is normalizable, which it will be for sufficiently small perturbations. For
λ = 1 we would find the solution for H(1) = H (0) + δH in the form

|ni ≡ |ni1 = |n(0) i + |n(1) i + |n(2) i + |n(3) i + . . . ,

(1.1.10)
En ≡ En (1) = En(0) + En(1) + En(2) + En(3) + . . .

Substituting the ansatz (1.1.7) into the Schrödinger equation (1.1.4) we will find the
conditions for such solution to exist:


H (0) + λδH − En (λ) |niλ = 0 , (1.1.11)

which more explicitly takes the form

 
(H (0) − En(0) ) − λ(En(1) − δH) − λ2 En(2) − λ3 En(3) − . . . − λk En(k) + . . .
  (1.1.12)
|n(0) i + λ|n(1) i + λ2 |n(2) i + λ3 |n(3) i + . . . + λk |n(k) i + . . . = 0 .
1.1. NONDEGENERATE PERTURBATION THEORY 5

Multiplying out we get a series in λ with coefficients λ-independent vectors in the state
space of the theory. If this is to vanish for all values of λ those coefficients must be zero.
Collecting the coefficients for each power of λ we

λ0 : (H (0) − En(0) ) |n(0) i = 0 ,

λ1 : (H (0) − En(0) ) |n(1) i = (En(1) − δH)|n(0) i ,

λ2 : (H (0) − En(0) ) |n(2) i = (En(1) − δH)|n(1) i + En(2) |n(0) i ,

λ3 : (H (0) − En(0) ) |n(3) i = (En(1) − δH)|n(2) i + En(2) |n(1) i + En(3) |n(0) i ,

.. .. ..
. . .

λk : (H (0) − En(0) ) |n(k) i = (En(1) − δH)|n(k−1) i + En(2) |n(k−2) i + . . . + En(k) |n(0) i .

(1.1.13)
Each equation is the condition that the coefficient multiplying the power of λ indicated to
the left vanishes. That power is reflected as the sum of superscripts on each term, counting
δH as having superscript one. This gives a simple consistency check on our equations. These
(1) (2)
are equations for the kets |n(1) i, |n(2) i, . . . as well as the energy corrections En , En , . . ..
Note again that λ does not enter into the equations, and thus the kets and energy corrections
are λ independent.
The first equation, corresponding to λ0 , is satisfied by construction. The second equa-
tion, corresponding to λ1 , should allow us to solve for the first correction |n(1) i to the state
(1)
and the first correction En to the energy. Once these are known, the equation corre-
(2)
sponding to λ2 involves only the unknowns |n(2) i and En , and should determine them. At
each stage each equation has only two unknowns: a state correction |n(k) i and an energy
(k)
correction En .

A useful choice. We now claim that without loss of generality we can assume that all the
state corrections |nk i, with k ≥ 1 contain no vector along |n(0) i. Explicitly:

0 = hn(0) |n(1) i = hn(0) |n(2) i = hn(0) |n(3) i = . . . . (1.1.14)

To show this we explain how we can manipulate a solution that does not have this
property into one that does. Suppose you have solution in which the state corrections |n(k) i
have components along |n(0) i:

|n(k) i = |n(k) i′ − ak |n(0) i, k ≥ 1, (1.1.15)

with some constants ak and with |n(k) i′ orthogonal to |n(0) i. Then the solution for the full
6 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

corrected state is



|niλ = |n(0) i + λ |n(1) i′ − a1 |n(0) i + λ2 |n(2) i′ − a2 |n(0) i + . . .

(1.1.16)
= 1 − a1 λ − a2 λ2 − . . . |n(0) i + λ|n(1) i′ + λ2 |n(2) i′ + . . .

Since this is an eigenstate of the Hamiltonian H(λ), it will still be an eigenstate if we change
its normalization by dividing it by any function of λ. Dividing by the coefficient of |n(0) i
we have the physically identical solution |ni′λ given by
1  
|ni′λ = |n(0) i +
λ|n(1) i′ + λ2 |n(2) i′ + . . . (1.1.17)
1 − a1 λ − a2 λ2 − . . .
We can expand the denominator so that we get


|ni′λ = |n(0) i + λ|n(1) i′ + λ2 |n(2) i′ + a1 |n(1) i′ + . . . (1.1.18)

The explicit expressions do not matter, the key point, actually visible in (1.1.17), is that
we have a physically identical solution of the same equation in which the state corrections
are all orthogonal to |n(0) i. This shows that we can impose the conditions (1.1.14) without
loss of generality.

Solving the equations. Let us finally begin solving equations (1.1.13). For this we note
that the Schrodinger equation for the ket |n(0) i implies that for the bra we have

hn(0) |(H (0) − En(0) ) = 0 . (1.1.19)

This means that acting with hn(0) | on the left-hand side of any of the equations in (1.1.13)
will give zero. Consistency requires that acting with hn(0) | on the right-hand side of any of
the equations in (1.1.13) also give zero, and presumably some interesting information. For
the λ-equation this gives:
0 = hn(0) |(En(1) − δH)|n(0) i . (1.1.20)
(1)
Since |n(0) i is normalized and En is a number, this means that

En(1) = hn(0) |δH|n(0) i . (1.1.21)

This is the most famous result in perturbation theory: the first correction to the energy of
an energy eigenstate is simply the expectation value of the correction to the Hamiltonian
in the uncorrected state. You need not know the correction to the state to determine the
first correction to the energy! Note that the hermicity of δH implies the required reality of
the energy correction.
We can actually find some interesting formulae (but not yet fully explicit!) for the higher
energy corrections. For the λ2 equation, acting with hn(0) | on the right-hand side gives
 
0 = hn(0) | (En(1) − δH)|n(1) i + En(2) |n(0) i . (1.1.22)
1.1. NONDEGENERATE PERTURBATION THEORY 7

(1)
Recalling our orthogonality assumption, we have hn(0) |n(1) i = 0 and the term with En
drops out. We get
En(2) = hn(0) |δH|n(1) i , (1.1.23)
which states that the second correction to the energy is determined if we have the first
correction |n(1) i to the state. Note that this expression is not explicit enough to make it
(2)
manifest that En is real. This and the earlier result for the first correction to the energy
have a simple generalization. Acting with hn(0) | on the last equation of (1.1.13) we get
 
0 = hn(0) | (En(1) − δH)|n(k−1) i + En(2) |n(k−2) i + . . . + En(k) |n(0) i . (1.1.24)

Using the orthogonality of |n(0) i and all the state corrections, we have

0 = −hn(0) |δH)|nk−1 i + En(k) , (1.1.25)

and therefore we have

En(k) = hn(0) | δH |n(k−1) i . (1.1.26)

At any stage of the recursive solution, the energy at a fixed order is known if the state
correction is known to previous order. So it is time to calculate the corrections to the
states!
Let us solve for the first correction |n(1) i to the state. This state must be some particular
superposition of the original energy eigenstates |k(0) i. For this we look at the equation

(H (0) − En(0) ) |n(1) i = (En(1) − δH)|n(0) i . (1.1.27)

This is a vector equation: the left-hand side vector set equal to the right-hand side vector.
As in any vector equation, we can check it using a basis set of vectors. Forming the inner
product of each and every basis vector with both the left-hand side and the right-hand side,
we must get equal numbers. We already acted on the above equation with hn(0) | to figure
(1)
out En . The remaining information in this equation can be obtained by acting with all
the states hk(0) | with k 6= n:

hk(0) |(H (0) − En(0) ) |n(1) i = hk(0) |(En(1) − δH)|n(0) i . (1.1.28)

On the left-hand side we can let H (0) act on the bra. On the right-hand side we note that
(1)
with k 6= n the term with En vanishes
(0)
(Ek − En(0) ) hk(0) | n(1) i = −hk(0) |δH|n(0) i . (1.1.29)

To simplify notation we define the matrix elements of δH in the original basis

δHmn ≡ hm(0) |δH|n(0) i . (1.1.30)

8 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

Note that the Hermiticity of δH implies that

δHnm = (δHmn )∗ . (1.1.31)
With this notation, equation (1.1.29) gives
δHkn
hk(0) | n(1) i = − (0) (0)
, k 6= n . (1.1.32)
Ek − En
Since we now know the overlap of |n(1) i with all basis states, this means that the state has
been determined. Indeed we can use the completeness of the basis to write
X X
|n(1) i = |k(0) ihk(0) |n(1) i = |k(0) ihk(0) |n(1) i , (1.1.33)
k k6=n

since the term with k = n does not contribute because of the orthogonality assumption.
Using the overlaps (1.1.32) we now get
X |k(0) iδHkn
|n(1) i = − (0) (0)
. (1.1.34)
k6=n Ek − En

This shows that the first correction |n(1) i can have components along all basis states, except
|n(0) i. The component along a state |k(0) i vanishes if the perturbation δH does not couple
|n(0) i to |k(0) i, namely, if δHkn vanishes. Note that the assumption of non-degeneracy is
needed here. We are summing over all states |k(0) i that are not |n(0) i and if any such state
has the same H (0) energy as |n(0) i the energy denominator will vanish causing trouble!
Now that we have the first order correction to the states we can compute the second
order correction to the energy. Using (1.1.23) we have
X hn(0) |δH|k(0) iδHkn
En(2) = hn(0) |δH|n(1) i = − (0) (0)
. (1.1.35)
k6=n Ek − En

In the last numerator we have hn(0) |δH|k(0) i = δHnk = (δHkn )∗ and therefore
X |δHkn |2
En(2) = − (0) (0)
. (1.1.36)
E
k6=n k − En

(2)
This is the second-order energy correction. This explicit formula makes the reality of En
manifest.
In summary, going back to (1.1.7), we have that the states and energies for H(λ) =
H (0) + λδH are, to this order,
X δHkn
|niλ = |n(0) i − λ (0) (0)
|k(0) i + O(λ2 ) ,
k6=n Ek − En
(1.1.37)
X |δHkn |2
En (λ) = En(0) + λ δHnn − λ 2
(0) (0)
3
+ O(λ ) ,
k6=n Ek − En
1.1. NONDEGENERATE PERTURBATION THEORY 9

Remarks:

1. The first order corrected energy of the (non-degenerate) ground state overstates the
true exact ground state energy. To see this consider the first order corrected ground
(0) (1)
state energy E0 + λE0 . Writing this in terms of expectation values, with |0(0) i
denoting the unperturbed ground state, we have
(0) (1)
E0 + λE0 = h0(0) |H (0) |0(0) i + λh0(0) |δH|0(0) i
= h0(0) |(H (0) + λδH)|0(0) i (1.1.38)
= h0(0) |H(λ)|0(0) i .

By the variational principle, the expectation value of the Hamiltonian on an arbitrary

(normalized) state is larger than the ground state energy E0 (λ), therefore

(0) (1)
E0 + λE0 = h0(0) |H(λ)|0(0) i ≥ E0 (λ) , (1.1.39)

which is what we wanted to prove. Given this overestimate at first order, the second
order correction to the ground state energy is always negative. Indeed,
X |δHk0 |2
− λ2 (0) (0)
, (1.1.40)
k6=0 Ek − E0

(0)
and each term is negative because the unperturbed excited state energies Ek (k 6= 0)
(0)
exceed the unperturbed ground state energy E0 .

2. The second order correction to the energy of the |n(0) i eigenstate exhibits level repul-
sion: the levels with k > n push the state down and the levels with k < n push the
state up. Indeed,
X |δHkn |2 X |δHkn |2 X |δHkn |2
− λ2 (0) (0)
= − λ2 (0) (0)
+ λ2 (0) (0)
. (1.1.41)
k6=n Ek − En k>n Ek − En k<n En − Ek

The first term gives the negative contribution from the higher energy states and the
second term gives the contribution from the lower energy states (see Figure 1.2).

The systematics of solving the equations is now apparent. For each equation we take
inner products with all states in the state space. That gives the full content of the equation.
We first take the inner product with hn(0) |, as this makes the left-hand side equal to zero
and is thus simpler. Then we take the inner product with hk(0) | with all k 6= n and that
gives the remainder of the information that is contained in the equation.
(3)
Exercise 1. Calculate |n(2) i and En .
10 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

Figure 1.2: The second order corrections to the energy of the state |n(0) i receives negative contri-
butions from the higher energy states and positive contributions from the lower energy states. We
have, effectively, a repulsion preventing the state |n(0) i from approaching the neighboring states.

Exercise 2. The state |niλ is not normalized. Use (1.1.37) to calculate to order λ2 the
quantity Zn (λ) defined by
1
≡ λ hn|niλ . (1.1.42)
Zn (λ)
What is the probability that the state |niλ will be observed to be along its unperturbed
version |n(0) i?

1.1.1 Validity of the perturbation expansion

We now return to a question we did not address: What do we mean when we say that
λδH is small? We have said that λδH must be small compared to the original Hamiltonian
H (0) , but it is not clear what this means, as both expressions are operators. For some
insight into this matter consider an example where H (0) is a two-by-two diagonal matrix
with non-degenerate eigenvalues
!
(0)
E1 0
H (0) = (0) . (1.1.43)
0 E2

The perturbation, called λV̂ , only has off-diagonal elements so that

!
(0)
(0) E1 λV
H(λ) = H + λV̂ ≡ ∗ (0) . (1.1.44)
λV E2
1.1. NONDEGENERATE PERTURBATION THEORY 11

In this simple example there is no need to use perturbation theory since the eigenvalues,
E+ and E− , can be calculated exactly as functions of λ
v " #2
u
1 (0) (0) 1 (0)
u
(0) t λ|V |
E± (λ) = 2 (E1 + E2 ) ± 2 (E1 − E2 ) 1 + (0) (0)
. (1.1.45)
1
2 (E1 − E2 )

The perturbative expansion of the energies is obtained by Taylor expansion of the square

√
Figure 1.3: The Taylor expansion of the function f (z) = 1 + z 2 about z = 0 has a radius of
convergence equal to one.

root in powers of λ. To perform this expansion we need the result

p z2 z4 z6 5 8
f (z) ≡ 1 + z2 = 1 + − + + z + O(z 10 ) . (1.1.46)
2 8 6 128
The function f (z) exhibits branch cuts at z = ±i (see Figure 1.3), thus the expansion
of f (z) around z = 0 has radius of convergence equal to one: the series converges for |z| < 1
and diverges for |z| > 1. Table 1 shows f (z) evaluated for z = 0.9, 1.2, and 1.5. The various
approximations to the full series are shown.
For our expansion of (1.1.45), convergence for |z| < 1 implies convergence when

|λ||V | (0) (0)

(0) (0)
< 1 =⇒ |λV | < 12 |E1 − E2 | . (1.1.47)
1
2 |E1 − E2 |

(0) (0)
For |λV | > 12 |E1 − E2 | the perturbation series does not converge. We learn that for
convergence the perturbation must be small compared with energy differences in H (0) . It
is not sufficient that the magnitude of the matrix elements of λδH be small compared to
those in H (0) , energy differences matter. This result leads us to expect complications when
energy differences go to zero and H (0) has degeneracies.
12 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

z 0.9 1.2 1.5

f (z) 1.34536 1.56205 1.80278
f8 (z) 1.33939 1.47946 1.20297
f14 (z) 1.33939 1.67280 4.82288
f20 (z) 1.34490 1.36568 -18.4895
f30 (z) 1.34545 2.23047 641.772
√ P i
Pn i.
Table 1.1: f (z) ≡ 1 + z2 = i ci z and fn (z) = i=0 ci z

1.1.2 Example: Anharmonic oscillator

Consider the simple harmonic oscillator
p̂2
H (0) = + 1 mω 2 x̂2 . (1.1.48)
2m 2
We want to explore the effect of a perturbation proportional to ∼ x̂4 . This has the effect
of changing the original quadratic potential for a more complicated potential that includes
a quartic term. To do analysis in a clear way, we must consider units. Using the constants
~, m, ω of the harmonic oscillator a length scale d can be uniquely build:
~
d2 = . (1.1.49)
mω
The unit-free coordinate x̂/d then has a simple expression in terms of creation and annihi-
lation operators:
r
~ x̂
x̂ = (â + ↠) = d √12 (â + ↠) → = √12 (â + ↠) . (1.1.50)
2mω d
It follows that an x̂4 perturbation with units of energy takes the form
x̂4 m2 ω 3 4
δH = ~ω = x̂ = 1
4 ~ω(â + ↠)4 . (1.1.51)
d4 ~
Using the unit-free parameter λ, the perturbed Hamiltonian will therefore be

m2 ω 3 4
H(λ) = H (0) + λ x̂ = H (0) + λ 41 ~ω(â + ↠)4 . (1.1.52)
~

We will identify the states |k(0) i of H (0) with the number eigenstates |ki, k = 0, 1, . . . , of
the harmonic oscillator. Recall that
(0) (↠)k
Ek = ~ω(k + 21 ) , |ki = √ |0i . (1.1.53)
k!
1.1. NONDEGENERATE PERTURBATION THEORY 13

The Hamiltonian H(λ) defines an anharmonic oscillator. In a classical anharmonic oscil-

lator the frequency of oscillation depends on the amplitude of oscillation. In the quantum
harmonic oscillator all levels are equally spaced. The frequencies associated with transi-
tions between various levels are therefore integer multiples (i.e. harmonics) of the basic
frequency associated to a transition between the first excited state and the ground state.
In the quantum anharmonic oscillator the spacing between the energy levels is not uniform.
(1)
First the simplest question: What is the first-order correction E0 to the energy of the
ground state? For this, following (1.1.21) we simply calculate the expectation value of the
perturbation on the ground state:
(1)
E0 = h0| 41 ~ω(â + ↠)4 |0i = 1
4 ~ωh0|(â + ↠)4 |0i = 3
4 ~ω , (1.1.54)

where we used
h0|(â + ↠)4 |0i = 3 , (1.1.55)
as you should verify. It follows that the corrected energy is
(0) (1)

E0 (λ) = E0 + λE0 + O(λ2 ) = 21 ~ω + λ 34 ~ω + O(λ2 ) = 1
2 ~ω 1 + 23 λ + O(λ2 ) (1.1.56)

We note that the energy of the ground state increases with λ > 0. This is reasonable as the
quartic term in the modified potential squeezes the ground state. How about second order
correction to the ground state energy? For this we use (1.1.36) taking n = 0:

(2)
X |δHk0 |2
E0 = − (0) (0)
. (1.1.57)
k6=0 Ek − E0

The sum is over all k ≥ 1 such that δHk0 is non-vanishing. Here

δHk0 = 1
4 ~ω hk|(â + ↠)4 |0i . (1.1.58)

We consider (â + ↠)4 |0i which corresponds, up to constants to acting on the ground state
wavefunction ϕ0 with x4 . This should give an even wavefunction. So (â + ↠)4 |0i must
be a superposition of |0i, |2i, and |4i. We cannot get states with higher number because
there are at most four creation operators acting on the vacuum. A short calculation (do
it!) confirms that √ √
(â + ↠)4 |0i = 3|0i + 6 2 |2i + 4! |4i . (1.1.59)
This immediately gives
√ √
3 3 2 6
δH00 = 4 ~ω , δH20 = 2 ~ω , δH40 = 2 ~ω , (1.1.60)

the first of which we had already determined and is not needed for the second order com-
putation. Back in (1.1.57) we have

(2) |δH20 |2 |δH40 |2 (~ω)2 9 (~ω)2 3 9 3

E0 = − − = − − =− 4 + 8 ~ω = − 21
8 ~ω . (1.1.61)
2~ω 4~ω 2~ω 2 4~ω 2
14 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

Therefor the corrected ground state energy to quadratic order is

(0) (1) (2)

E0 + λE0 + λ2 E0 = 1
2 ~ω 1 + 32 λ − 21 2
4 λ . (1.1.62)

The computation can be carried to higher order, as first done by Bender and Wu (Phys.
Rev.184 (1969)1231). They find that1
2 333 3 30885 4 916731 5 65518401 6 7


E0 (λ) = 21 ~ω 1 + 32 λ − 21
4 λ + 8 λ − 64 λ + 128 λ − 512 λ + O(λ )
(1.1.63)
As it turns out the coefficients keep growing and the series does not converge for any nonzero
λ; the radius of convergence is actually zero! This does not mean the series is not useful.
It is an asymptotic expansion. This means that for a given small value of λ the magnitude
of successive terms generally decrease until, at some point, they start growing again. A
good approximation to the desired answer is obtained by including only the part of the sum
where the terms are decreasing.
(1)
Exercise 3. Calculate the first order correction En to the energy for the state |ni of
number n. Exhibit the anharmonicity of the oscillator by using this result to find, to first
order in λ, the energy separation ∆En (λ) = En (λ) − En−1 (λ) between levels.
Let us now find the first order correction to the ground-state wavefunction. Using
(1.1.34) with n = 0 we have
X δHk0
|0(1) i = − (0) (0)
|ki . (1.1.64)
k6=0 Ek − E0

We then find
δH20 δH40 √ √
|0(1) i = − |2i − |4i = − 34 2|2i − 1
16 4!|4i
2~ω 4~ω (1.1.65)
† † † † † †
= − 34 â â |0i − 1
16 â â â â |0i .
This means that to first order the ground state of the perturbed oscillator is
 
|0iλ = |0i − λ 3
4 ↠↠|0i + 1
16 ↠↠↠↠|0i + O(λ2 ) . (1.1.66)

1.2 Degenerate perturbation theory

If the spectrum of H (0) has degenerate states, as shown in Figure 1.1, tracking the evolution
of those states as λ becomes nonzero presents new challenges. We first show that naive
extrapolation of our results for a non-degenerate state do not work. We will also be able to
appreciate the basic difficulty.
1
Bender and Wu’s results, in eqns. (2.12) of their paper must all be multiplied by a factor of 2, as they
take A0 = 1/2.
1.2. DEGENERATE PERTURBATION THEORY 15

1.2.1 Degenerate toy model

Consider an example with two-by-two matrices. The unperturbed matrix H (0) will be set
equal to the identity matrix:  
(0) 1 0
H = . (1.2.1)
0 1
We have a degeneracy here as the two eigenvalues are identical (and equal to one). The
perturbation matrix δH is chosen to be off diagonal:
 
0 1
δH = . (1.2.2)
1 0

We then have  
(0) 1 λ
H(λ) = H + λδH = . (1.2.3)
λ 1
Using labels n = 1, 2 the unperturbed eigenstates can be taken to be
   
(0) 1 (0) 0 (0) (0)
|1 i = , |2 i = , E1 = E2 = 1 , (1.2.4)
0 1

with the corresponding eigenvalues indicated as well. To first order in λ, the eigenvalues
(0)
predicted from non-degenerate perturbation theory (1.1.37) are En (λ) = En + λδHnn .
This gives
(0)
E1 (λ) = E1 + λδH11 = 1 + λ · 0 = 1 ?
(0)
(1.2.5)
E1 (λ) = E2 + λδH22 = 1 + λ · 0 = 1 ?

The eigenvalues are unperturbed to first order in λ since the matrix δH is off-diagonal.
These answers, however, are wrong. We can compute the exact eigenvalues of H(λ) and
they are 1 ± λ. There is also a problem with the state corrections. Equation (1.1.37) states
that
X δHkn
|niλ = |n(0) i − λ (0) (0)
|k(0) i . (1.2.6)
E
k6=n k − En

(0) (0)
but this time, with E1 = E2 the denominator is zero, and the δH matrix element is also
zero, giving us an ambiguous result.
So what can we do? A direct calculation shows that
 
1 1
H(λ) has eigenvectors √ with eigenvalue = 1 + λ , (1.2.7)
2 1
 
1 1
and √ with eigenvalue = 1 − λ . (1.2.8)
2 −1

You may think the eigenvectors jump from those of H (0) indicated in (1.2.4) to those of
H(λ) as soon as λ becomes nonzero. Such discontinuity is totally against the spirit of
16 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

perturbation theory. Happily, this is not really true. The eigenvectors of H (0) are in fact
ambiguous, precisely due to the degeneracy. The eigenvectors of H (0) are actually the span
of the two vectors listed in (1.2.4). The perturbation selected a particular combination
of these eigenvectors. This particular combination is the one that we should use even for
λ = 0. The lesson is that to get states that vary continuously as λ is turned on we must
choose the basis in the degenerate subspace of H (0) carefully. We will call that carefully
selected basis the “good” basis.

1.2.2 Systematic Analysis

Again, we are looking at the perturbed Hamiltonian

H(λ) = H (0) + λδH , (1.2.9)

where H (0) has known eigenvectors and eigenvalues. We will focus this time on a degenerate
subspace of eigenvectors of dimension N > 1, that is, a space with N linearly independent
eigenstates of the same energy. In the basis of eigenstates, H (0) is a diagonal matrix that
contains a string of N > 1 identical entries:
(0) (0)
H (0) = diag { E1 , E2 , . . . , En(0) , . . . , En(0), . . . } . (1.2.10)
| {z }
N

In the degenerate subspace we choose a collection of N orthonormal eigenstates

|n(0) ; 1i , |n(0) ; 2i, . . . , |n(0) ; N i . (1.2.11)

Accordingly, we have

hn(0) ; p |n(0) ; li = δp,l , (1.2.12)

H (0) |n(0) ; ki = En(0) |n(0) ; ki . (1.2.13)

This set of vectors span a degenerate subspace of dimension N that we will call VN

VN ≡ span{|n(0) ; ki, k = 1, . . . N } . (1.2.14)

The total state space of the theory, denoted by H is written as a direct sum:

H = VN ⊕ V̂ , (1.2.15)

where V̂ is spanned by those eigenstates of H (0) that are not in VN . We denote by |p(0) i
with p ∈ Z a basis for V̂ . That basis may include both degenerate and non degenerate
states. Together with the states in VN we have an orthonormal basis for the whole state
space:
hp(0) |q (0) i = δpq , hp(0) |n(0) ; ki = 0 . (1.2.16)
1.2. DEGENERATE PERTURBATION THEORY 17

Our notation distinguishes the states in VN from those in V̂ because the former have two
labels and the latter have only one.
We now consider the evolution of the degenerate eigenstates as we turn on the pertur-
bation. Again we assume that the states vary continuously in λ and thus write:

|n(0) ; ki → |n; kiλ = |n(0) ; ki + λ|n(1) ; ki + λ2 |n(2) ; ki + O(λ3 ) ,

(1.2.17)
(1) (2)
En(0) → En,k (λ) = En(0) + λ En,k +λ 2
En,k 3
+ O(λ ) .

These equations hold for k = 1, . . . , N . Note that for each value of k the energy corrections
might be different and that’s why the energy corrections carry the label k. Our goal is to
(p)
find the state corrections |n(p) ; ki and the energy corrections En,k for p ≥ 1 and for each k.
As before we demand that |n(p) ; ki for p ≥ 1 has no component along |n(0) ; ki, i.e.

hn(0) ; k|n(p) ; ki = 0 for p ≥ 1 (1.2.18)

Note, however, that |n(p) ; ki may have components along |n(0) ; ℓi with ℓ 6= k. So |n(0) ; ki
may and in fact will have a component in VN .
The perturbed eigenstates must satisfy

H(λ) |n; kiλ = En,k (λ) |n; kiλ , (1.2.19)

and substituting the perturbative expansions above we obtain equations completely analo-
gous to the ones in Eq.(1.1.13)

λ0 : (H 0 − En(0) ) |n(0) ; ki = 0 , (1.2.20)

(1)
λ1 : (H 0 − En(0) ) |n(1) ; ki = (En,k − δH)|n(0) ; ki , (1.2.21)
(1) (2)
λ2 : (H 0 − En(0) ) |n(2) ; ki = (En,k − δH)|n(1) ; ki + En,k |n(0) ; ki , (1.2.22)
.. .. ..
. . .

In the following we will discuss a solution to first order for the case in which the de-
generacy in VN is completely broken to first order in perturbation theory; that is, the first
order corrections to the energies split the N states completely. Our solution will proceed
in three steps:

1. Hit the O(λ) equation with hn(0) ; ℓ| to learn that δH must be diagonal in the chosen
basis for VN and to determine the first-order energy shifts.

2. Use the O(λ) equation to calculate the components of |n(1) ; ki in V̂ .

3. Hit the O(λ2 ) equation with hn(0) ; ℓ| to determine the second order energy correction
(2)
En,k and the component of |n(1) ; ki in VN .
18 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

(0)
Step 1. Recalling that hn(0) ; ℓ|(H (0) − En ) = 0, as we hit the O(λ) equation with hn(0) ; ℓ|
the left-hand side vanishes and we find
(1)
hn(0) ; ℓ|(En,k − δH)|n(0) ; ki = 0 . (1.2.23)
Since the basis states in VN are orthonormal, this implies that
(1)
hn(0) ; ℓ| δH |n(0) ; ki = En,k δℓ,k . (1.2.24)
This equation holds for all k, ℓ = 1, . . . , N . Remarkably, this equation is telling us that the
basis |n(0) ; ki must be chosen to make the matrix δH diagonal in the subspace VN ! This
is required in order to get the perturbation theory going. Setting ℓ equal to k we read the
values of the first order energy shifts
(1)
En,k = hn(0) ; k|δH|n(0) ; ki = δHnk,nk , (1.2.25)
where the last equality is a definition. The energies to first order are then

En,k (λ) = En(0) + λ δHnk,nk . (1.2.26)

A few remarks:
1. The above result for the first order energy shifts is true always, even if the degeneracy
is not lifted. The degeneracy is lifted when
(1) (1)
En,k 6= En,ℓ , whenever k 6= ℓ , (1.2.27)
for all values of k, ℓ = 1, . . . , N . This assumption will be used in the later steps. If
the degeneracy is lifted, the basis states |n(0) ; ki that make δH diagonal in VN are
called “good states” or a “good basis”. This means that they are the basis states in
VN that get deformed continuously as λ becomes non-zero. If the degeneracy is not
lifted to first order the determination of the good basis has to be attempted to second
order.
2. The perturbation δH is diagonalized in the subspace VN . The perturbation δH is
not diagonal on the whole space H, only within the block representing VN is δH a
diagonal matrix. Alternatively we can see this via the action of δH on the basis states.
Introducing a resolution of the identity, we have
X X
δH|n(0) ; ℓi = |n(0) ; qi hn(0) ; q|δH|n(0) ; ℓi + |p(0) i hp(0) |δH|n(0) ; ℓi
q p
X (1)
X
= En,ℓ δℓ,q |n(0) ; qi + |p (0)
i hp (0)
|δH|n(0) ; ℓi (1.2.28)
q p
(1)
X
= En,ℓ |n(0) ; ℓi + |p(0) i hp(0) |δH|n(0) ; ℓi .
p

This shows that the states |n(0) ; ℓi are almost δH eigenstates with eigenvalues equal
to the first order energy corrections. The failure is an extra state along V̂ .
1.2. DEGENERATE PERTURBATION THEORY 19

3. We can sometimes assess without computation that a certain basis in VN makes δH

diagonal. Here is a rule: the matrix δH is diagonal for a choice of basis in VN if there
is a Hermitian operator K that commutes with δH for which the chosen basis vectors
are K eigenstates with different eigenvalues. This is quickly established. Consider
two different basis states in VN : |n(0) ; pi and |n(0) ; qi, with p 6= q. Assume these have
K eigenvalues λp and λq , respectively. Since [δH, K] = 0:

0 = hn(0) ; p|[δH, K]|n(0) ; qi = (λq − λp )hn(0) ; p| δH |n(0) ; qi . (1.2.29)

Since the eigenvalues λp and λq are presumed to be different, the non-diagonal matrix
elements of δH vanish.

Step 2. The O(λ) equation cannot determine the component of |n(1) ; ki along VN . As
we will see later, such piece is required by consistency and gets determined from the O(λ2 )
equation. We now determine the piece of |n(1) ; ki along V̂ . For this we hit the O(λ) equation
with hp(0) | to find
|p(0) i ⊥ VN
(1)
hp(0) |(H (0) − En(0) )|n(1) ; ki = hp(0) | ( En,k − δH ) |n(0) ; ki (1.2.30)

and we get
(Ep(0) − En(0) )hp(0) |n(1) ; ki = −δHp,nk , (1.2.31)
where we introduced the matrix element δHp,nk ≡ hp(0) | δH |n(0) ; ki. Our equation above
means that the piece of |n(1) ; ki in V̂ is now determined:
X δHp,nk
|n(1) ; ki = − (0) (0)
|p(0) i + |n(1) ; ki , (1.2.32)
Ep − En VN
p

where we included explicitly the still undetermined piece of |n(1) ; ki along VN .

Step 3. We now hit we hit the O(λ2 ) equation with hn(0) ; ℓ|. The left-hand side vanishes
and using the above expression for |n(1) ; ki we find

(1)
X δHp,nk
0 = − hn(0) ; ℓ|(En,k − δH) |p(0) i (0) (0)
p Ep − En
(1.2.33)
(0) (1) (1) (2)
+ hn ; ℓ|(En,k − δH)|n ; ki +En,k δk,ℓ .
VN

(1)
In the first term on the right-hand side, the part proportional to En,k vanishes by orthonor-
mality. On the second line, the term including δH can be simplified because δH is diagonal
within VN . Recalling (1.2.28) we have
(1)
X
hn(0) ; ℓ|δH = En,ℓ hn(0) ; ℓ| + hn(0) ; ℓ|δH|p(0) i hp(0) | . (1.2.34)
p
20 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

The piece in V̂ vector drops out for our case of interest:

(1)
hn(0) ; ℓ|δH|n(1) ; ki = En,ℓ hn(0) ; ℓ|n(1) ; ki . (1.2.35)
VN VN

Back into equation (1.2.33) we now get

X δHnℓ,p δHp,nk  (1) (1)

(2)
(0) (1)
(0) (0)
+ En,k − En,ℓ hn ; ℓ|n ; ki + En,k δk,ℓ = 0 . (1.2.36)
Ep − En VN
p

Setting ℓ = k we can determine the second correction to the energies:

(2)
X |δHp,nk |2
En,k = − (0) (0)
. (1.2.37)
p E p − En

For k 6= ℓ we get
X δHnℓ,p δHp,nk  
(1) (1)
(0) (0)
+ En,k − En,ℓ hn(0) ; ℓ|n(1) ; ki = 0. (1.2.38)
Ep − En VN
p

Had we not included the piece of |n(1) ; ki along the degenerate subspace we would have
had an inconsistency, since there is no reason why the first term on the left-hand side must
be zero. Now the above equation just fixes the components of |n(1) ; ki in the degenerate
(1) (1)
subspace as long as En,k 6= En,ℓ :
1 X δHnℓ,p δHp,nk
hn(0) ; ℓ|n(1) ; ki = − (1) (1) (0) (0)
, k 6= ℓ. (1.2.39)
VN En,k − En,ℓ Ep − En
p

We thus have
X 1 X δHnℓ,p δHp,nk
|n(1) ; ki = − |n(0) ; ℓi (1) (1) (0) (0)
. (1.2.40)
VN En,k − En,ℓ Ep − En
ℓ6=k p

It may seem that this extra piece, found by using the O(λ2 ) equation, is higher order than
it should in the perturbation: its numerator contains two powers of δH. But this expression
(1) (1)
also has a curious energy denominator, En,k − En,ℓ , in which each term has a power of δH.
All in all, the correction to the state is properly first order in δH.
Summarizing our result we have

Degenerate perturbation theory with degeneracies lifted at O(λ):

X δHp,nk X |n(0) ; ℓi X δHnℓ,p δHp,nk 
|n; kiλ = |n(0) ; ki − λ (0) (0)
|p(0) i + (1) (1) (0) (0)
+ O(λ2 )
p Ep − En ℓ6=k En,k − En,ℓ p Ep − En
X δHnk,p δHp,nk (1)
En,k (λ) = En(0) + λ δHnk,nk − λ2 (0) (0)
+ O(λ3 ) , En,k = δHnk,nk .
p Ep − En
(1.2.41)
1.2. DEGENERATE PERTURBATION THEORY 21

1.2.3 Degeneracy lifted at second order

We now investigate the case when the degeneracy is completely unbroken to first order.
The situation and the setup is similar to the one we just considered: we have a degenerate
subspace VN of dimension N and the rest of the space is called V̂ . This time, however, we
will assume that the degeneracy of H (0) is not broken to first order in the perturbation δH.
Concretely, this means that on the VN basis |n(0) ; ki with k = 1, . . . , N , we have

hn(0) ; ℓ| δH |n(0) ; ki = En(1) δℓ,k . (1.2.42)

(1)
The first order energy correction is the same, and equal to En , for all basis states in VN .
You should compare with (1.2.24), where the energy had an extra subscript to distinguish
its various possible values.
Because the degeneracy is not broken to first order we do not know at this point what
is the good basis in VN . We will consider here the case when the degeneracy is completely
lifted to second order. We express our ignorance about good basis vectors by stating that
we are searching for the right linear combinations:
N
X (0)
|ψ (0) i = |n(0) ; ki ak . (1.2.43)
k=1

(0)
For some values of the constants ak with k = 1, . . . , N the state |ψ (0) i will be good. We
can think of a(0) as the column vector representation of |ψ (0) i in VN . We have written
just one state, |ψ (0) i, even though we are expecting to find N good states to span the
degenerate subspace. We therefore adjust the notation to reflect this. We introduce a new
index I = 1, . . . , N and write
N
X
(0) (0)
|ψI i = |n(0) ; ki aIk , I = 1, . . . , N . (1.2.44)
k=1

The index I now labels the different good states and their different vector representations
(0) (0)
aI . Our most immediate goal is to find those vectors aI and thus the good basis. To
(0)
do so we will have to consider second order energy corrections. The states |ψI i form an
(0)
orthonormal basis in VN if the coefficients aI satisfy

(0) (0)
X (0) (0)
hψJ |ψI i = δIJ → (aJk )∗ aIk = δIJ . (1.2.45)
k

We set up the perturbation theory as usual

(0) (1) (2)
|ψI iλ = |ψI i + λ|ψI i + λ2 |ψI i + . . . ,
(1.2.46)
(2) (3)
EnI (λ) = En(0) + λ En(1) +λ 2
EnI +λ 3
EnI + ... .
22 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

Note that in the energy expansion we have accounted for the degeneracy to zeroth and first
order: the index I first appears in the second-order corrections to the energy. Using the
Schrödinger equation
H(λ)|ψI iλ = EnI (λ)|ψI iλ , (1.2.47)
gives the by now familiar equations, of which we list the first four:
(0)
λ0 : (H (0) − En(0) ) |ψI i = 0 ,
(1) (0)
λ1 : (H (0) − En(0) ) |ψI i = (En(1) − δH)|ψI i ,
(1.2.48)
(2) (1) (2) (0)
λ2 : (H (0) − En(0) ) |ψI i = (En(1) − δH)|ψI i + EnI |ψI i ,
(3) (2) (2) (1) (3) (0)
λ3 : (H (0) − En(0) ) |ψI i = (En(1) − δH)|ψI i + EnI |ψI i + EnI |ψI i .

The zero-th order equation is trivially satisfied. For the order λ equation the overlap with
hn(0) ; ℓ| works out automatically, without giving any new information. Indeed, the left-hand
side vanishes and we thus get
(0)
0 = hn(0) ; ℓ|(En(1) − δH)|ψI i . (1.2.49)
(1)
Since hn(0) ; ℓ| is a δH eigenstate with eigenvalue En , up to a vector in V̂ (see (1.2.34)),
the above right-hand side vanishes. Acting on the order λ equation with hp(0) | gives useful
information:
(1) (0) (0)
(Ep(0) − En(0) )hp(0) |ψI i = hp(0) |(En(1) − δH)|ψI i = −hp(0) |δH|ψI i , (1.2.50)

using the orthogonality of V̂ and VN . Letting

(0)
δHpI ≡ hp(0) |δH|ψI i , (1.2.51)

we then have
(1) δH pI
hp(0) |ψI i = − (0) (0)
. (1.2.52)
Ep − En
(0)
Since the ket |ψI i is still undetermined, it makes sense to write this information about
(1) (0)
|ψI i in terms of the unknown aI coefficients. We have
N
X N
X
(0) (0)
δHpI ≡ hp(0) |δH|n(0) ; kiaIk = δHp,nk aIk , (1.2.53)
k=1 k=1

Back into (1.2.52) we get

N
(1) 1 X (0)
hp(0) |ψI i = − (0) (0)
δHp,nk aIk . (1.2.54)
Ep − En k=1
1.2. DEGENERATE PERTURBATION THEORY 23

(1)
This gives the piece of |ψI i in V̂ in terms of the unknown zeroth order eigenstates.
We have now extracted all the information from the order λ equation. We look now
at the order λ2 equation, which contains the second order corrections to the energy and
therefore should help us determine the zeroth order good states. We hit that equation with
hn(0) ; ℓ| and we get
(1) (1) (2) (0)
0 = hn(0) ; ℓ|(En(1) − δH)|ψI i +hn(0) ; ℓ|(En(1) − δH)|ψI i + EnI aIℓ . (1.2.55)
V̂ VN

(1)
Happily, the second term, involving the components of |ψI i along VN , vanishes because
(1)
of the by now familiar property (1.2.28) adapted to this case. The piece with En on the
first term also vanishes. We are thus left with
(1) (2) (0)
0 = −hn(0) ; ℓ|δH|ψI i + EnI aIℓ . (1.2.56)
V̂

Introducing a resolution of the identity to the immediate right of δH, only the basis states
in V̂ contribute and we get
X (1) (2) (0)
0 = − hn(0) ; ℓ|δH|p(0) ihp(0) |ψI i + EnI aIℓ , (1.2.57)
p

where there is no need to copy the |V̂ anymore. Using the result in (1.2.54) we now get
N N
X 1 X (0)
X (2) (0)
0 = δHnl,p (0) (0)
δHp,nk aIk + EnI δℓk aIk (1.2.58)
p Ep − En k=1 k=1

Reordering sums and multiplying by minus one we get

N
!
X X δHnl,p δHp,nk (2) (0)
− (0) (0)
− EnI δℓk aIk = 0 . (1.2.59)
k=1 p Ep − En

To understand better this equation we define the N × N Hermitian matrix M (2)

(2)
X δHnℓ,p δHp,nk
Mℓ,k ≡ − (0) (0)
. (1.2.60)
p Ep − En

The equation then becomes

N 
X 
(2) (2) (0)
Mℓ,k − EnI δℓk aIk = 0 . (1.2.61)
k=1

Recalling that the Kronecker delta is the matrix representation of the identity, we have
 
(2) (0)
M (2) − EnI 1 aI = 0 . (1.2.62)
24 CHAPTER 1. TIME INDEPENDENT PERTURBATION THEORY

(2)
This is an eigenvalue equation that tells us that the energy corrections EnI are the eigen-
(0)
values of M (2) and the vectors aI are the associated normalized eigenvectors. These
determine, via (1.2.44), our orthonormal basis of good zeroth order states. If δH is known,
the matrix M (2) is computable and Hermitian and can therefore be diagonalized.
(1)
We will leave the computation of the component of |ψI i on the degenerate subspace.
That can be done if the degeneracy is completely broken to quadratic order (the eigenvalues
of M (2) are all different). Still, it takes some effort and one must use the order λ3 equation.
Our results so far are
X δHpI X (0) (1) 
(0)
|ψI iλ = |ψI i + λ |p(0) i (0) (0)
+ |ψJ i aI,J + O(λ2 ) ,
p En − Ep J6=I (1.2.63)
(2) (3)
EIn (λ) = En(0) + λ En(1) + λ2 EIn + λ3 EIn + . . . O(λ3 ) .

(1)
Here the aI,J are still unknown coefficients that determine the component of the first cor-
rection to the states along the degenerate subspace. If you followed the discussion, all other
symbols in the above equations have been defined and are computable given δH.
(1)
The answer for the coefficients aI,J turns out to be
" #
(1) 1 X δHJp δHpq δHqI X δHJp δHpI
aI,J = (2) (2) (0) (0) (0) (0)
− En(1) (0) (0)
2
. (1.2.64)
EnI − EnJ p,q (Ep − En )(Eq − En ) p Ep − En

The third order corrections to the energy are

(3)
X δHIp δHpq δHqI X |δHpI |2
EIn = (0) (0) (0) (0)
− En(1) (0) (0)
2
. (1.2.65)
p,q (Ep − En )(Eq − En ) p Ep − En
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Chapter 2

Fine Structure

c B. Zwiebach

2.1 Review of hydrogen atom

The hydrogen atom Hamiltonian is by now familiar to you. You have found the bound state
spectrum in more than one way and learned about the large degeneracy that exists for all
states except the ground state. We will call the hydrogen atom Hamiltonian H (0) and it is
given by
p2 e2
H (0) = − . (2.1.1)
2m r
We take this to be the “known” Hamiltonian, meaning that we know its spectrum. This
Hamiltonian is supplemented with corrections that can be studied in perturbation theory.
That study is the subject of this chapter. We begin, however, with some review and
comments.
The mass m in H (0) is the reduced mass of the electron and proton, which we can
accurately set equal to the mass of the electron. If one wishes to consider the case of an an
electron bound to a nucleus with Z protons one lets e2 → Ze2 in H (0) . The Bohr radius is
the length scale build from ~, m, and e2

~2
a0 ≡ ∼ 53 pm. (2.1.2)
me2
The energy levels are enumerated using a principal quantum number n, an integer that
must be greater or equal to one:

e2 1
En = − , n = 1, 2, . . . . (2.1.3)
2a0 n2

Note that H (0) is a non-relativistic Hamiltonian: the speed of light does not enter in it,
and the kinetic term is that of Newtonian mechanics. The energy scale relevant to the

25
26 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

bound state spectrum can be better appreciated using the speed of light to consider both
the fine structure constant and the rest energy of the electron. The fine structure constant
is given by
e2 1
α ≡ ≃ , (2.1.4)
~c 137
and the rest energy of the electron is mc2 . Then,

e2 me4 mα2 ~2 c2
= = = α2 mc2 . (2.1.5)
a0 ~2 ~2

This states that the energy scale of hydrogen bound states is a factor of α2 smaller than
the rest energy of the electron, that is, about 19000 times smaller. We can thus rewrite the
possible energies as:
1
En = − 12 α2 mc2 2 . (2.1.6)
n
The typical momentum in the hydrogen atom is

~ me2 e2
p ≃ = = mc → p ≃ α(mc) , (2.1.7)
a0 ~ ~c

which, written as p ≃ m(αc) says that the typical velocity is v ≃ αc, which is low enough
that the non-relativistic approximation is fairly accurate. Finally, we note that

~2 ~ 1 λ̄
a0 = = = , (2.1.8)
m α~c mc α α
which says that the Bohr radius is over a hundred times bigger than the (reduced) Compton
wavelength of the electron.
The degeneracy of the hydrogen atom spectrum is completely quantified by the relation

n = N + ℓ + 1. (2.1.9)

Here N ≥ 0 is the degree of a polynomial in r that appears in a wavefunction where the

leading dependence on r near the origin is factored out. The quantum number ℓ ≥ 0 is the
angular momentum of the state. For each fixed n, you can see that the number ℓ ranges
from zero to n − 1. And for each fixed ℓ the eigenvalue of Lz is m~ with m ranging from
−ℓ up to ℓ:

n = 1, 2, . . . ℓ = 0, 1, . . . , n − 1
n−1
X
m = −ℓ, . . . , ℓ # of states with energy En = (2ℓ + 1) = n2
ℓ=0

The states of hydrogen are shown in this energy diagram, which is not drawn to scale,
2.1. REVIEW OF HYDROGEN ATOM 27

S P D F
ℓ=0 ℓ=1 ℓ=2 ℓ=3
.. .. .. .. ..
. . . . .

n=4
N =3 N =2 N =1 N =0

n=3
N =2 N =1 N =0

n=2
N =1 N =0

n=1
N =0

The table features the commonly used notation where capital letters are used to denote
the various values of the orbital angular momentum ℓ. If we have L denote the generic
capital letter for angular momentum we have L(ℓ) where

L(ℓ = 0) = S , L(ℓ = 1) = P , L(ℓ = 2) = D , L(ℓ = 3) = F , . . . . (2.1.10)

Thus, for example, an S state is a state with ℓ = 0, a P state is a state with ℓ = 1, and a
D state is a state with ℓ = 2.
Any hydrogen eigenstate specified by the three quantum numbers n, ℓ, m, because, as it
follows from (2.1.9), the value of N is then fixed. The wavefunction takes the form
 ℓ  
r r − r
ψn,ℓ,m (x) = A · Polynomial in of degree N · e na0 Yℓ,m (θ, φ) , (2.1.11)
a0 a0
where A is a normalization constant and N = n − (ℓ + 1). If you look at the wavefunction,
the value of n can be read from the exponential factor. The value of ℓ can be read from
the radial prefactor, or from the spherical harmonic. The value of m can be read from
the spherical harmonic. For the ground state n = 1, ℓ = 0 and m = 0. The normalized
wavefunction is
1 − r
ψ1,0,0 (r) = p 3 e a0 . (2.1.12)
πa0

Comments:
1. There are n2 degenerate states at any energy level with principal quantum number
n. This degeneracy explained by the existence of a conserved quantum Runge-Lenz
vector. For a given n the states with various ℓ’s correspond, in the semiclassical
picture, to orbits of different eccentricity but the same semi-major axis. The orbit
with ℓ = 0 is the most eccentric one and the orbit with maximum ℓ = n − 1 is the
most circular one.
28 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

2. For each fixed value of ℓ, the states have increasing N as we move up in energy. The
number N is the number of nodes in the solution of the radial equation, that’s why
it is the degree of the polynomial in r that features in the wavefunction (2.1.11).

3. The analysis of H (0) so far ignored electron spin. Since the electron is a spin one-
half particle there is an extra degeneracy: each of the H (0) eigenstates is really two
degenerate states, one with the electron spin up and the other with the electron spin
down. These states are degenerate because H (0) has no spin dependence.

4. We will have to supplement H (0) with terms that correspond to corrections that arise
from relativity and from the spin of the electron. This will be the main subject of
the following analysis. It will determine the fine-structure of the hydrogen atom. The
corrections will break much of the degeneracy of the spectrum.

5. In order to understand better the spectrum and the properties of the Hydrogen atom
one can apply an electric field, leading to the Stark effect or a magnetic field, leading
to the Zeeman effect. These external fields are represented by extra terms in the
hydrogen atom Hamiltonian.
Let us now discuss two different choices of basis states for the hydrogen atom, both of
which include the electron spin properly.
Recall that, in general, for a multiplet of angular momentum j, we have states (j, mj ),
with mj running from −j to j in integer steps. All states in the multiplet are Ĵ2 eigenstates
with eigenvalue ~2 j(j + 1) and, for each state, ~mj is the eigenvalue of Jˆz .
Because the electron has spin one half, its states are labeled as
1
(s, ms ) , with s= 2 , ms = ± 12 . (2.1.13)

In the hydrogen atom the angular momentum ℓ can take different values, but the spin of
the electron is always one-half. As a result, the label s is often omitted, and we usually only
record the value of ms . For hydrogen basis states we thus have quantum numbers n, ℓ, mℓ ,
and ms . To avoid confusion, we have added the ℓ subscript to mℓ , thus emphasizing that
this is the azimuthal quantum number for orbital angular momentum. Since we are not
combining the electron spin to its orbital angular momentum, the states form the “uncoupled
basis”:

Uncoupled basis quantum numbers: (n, ℓ, mℓ , ms ) . (2.1.14)

The states are completely specified by these quantum numbers. As we let those quantum
numbers run over all possible values we obtain an orthonormal basis of states.
It is often useful to use an alternative basis where the states are eigenstates of Ĵ2 and Jˆz ,
where the total angular momentum Ĵ is obtained by adding the orbital angular momentum
L̂ to the spin angular momentum Ŝ:

Ĵ = L̂ + Ŝ . (2.1.15)
2.1. REVIEW OF HYDROGEN ATOM 29

When we form ℓ ⊗ s we are tensoring a a full ℓ multiplet to an s multiplet (here, of course,

s = 1/2). All states in ℓ ⊗ s are eigenstates of L̂2 and eigenstates of Ŝ2 , so ℓ and s are good
(constant) quantum numbers for all j multiplets that arise in the tensor product. Each j
multiplet has states with quantum numbers (j, mj ).
The coupled basis is one where states are organized into j multiplets. While states are
no longer L̂z nor Ŝz eigenstates they are still L̂2 eigenstates, thus the ℓ quantum number
survives. The coupled basis quantum numbers are therefore

Coupled basis quantum numbers: (n, ℓ, j, mj ) . (2.1.16)

The (mℓ , ms ) quantum numbers of the uncoupled basis have been traded for (j, mj ) quan-
tum numbers and we have kept the n, ℓ quantum numbers. The coupled states are linear
combinations of uncoupled states that involve different values of mℓ and ms , those combi-
nations that yield the same value of mj = mℓ + ms .
To find the list of coupled basis states we must tensor each ℓ multiplet in the hydrogen
atom spectrum with the spin doublet 12 . The rules of addition of angular momentum imply
that we find two j multiplets:
1
ℓ⊗ 2 = (j = ℓ + 21 ) ⊕ (j = ℓ − 12 ) . (2.1.17)

For ℓ = 0, we only obtain a j = 1/2 multiplet. We use the notation Lj for the coupled
multiplets, with L = S, P, D, F for ℓ = 0, 1, 2, and 3 (see (2.1.10). The change of basis is
summarized by the replacements
1
ℓ⊗ 2 → L(ℓ) 1 ⊕ L(ℓ) 1 (2.1.18)
j=ℓ+ 2 j=ℓ− 2

or more explicitly,
1
0⊗ 2 → S1
2
1
1⊗ 2 → P3 ⊕ P1
2 2
(2.1.19)
1
2⊗ 2 → D5 ⊕ D3
2 2
1
3⊗ 2 → F7 ⊕ F5
2 2

Thus, by the time we combine with electron spin, each ℓ = 0 state gives one j = 21 multiplet,
each ℓ = 1 state gives j = 23 and j = 21 multiplets, each ℓ = 2 state gives j = 25 and j = 32
multiplets, and so on. For hydrogen, the principal quantum number is placed ahead to
denote the coupled multiplets by

Coupled basis notation for multiplets: nLj (2.1.20)

Using this notation for coupled basis multiplets the diagram of hydrogen atom energy
eigenstates becomes:
30 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

S P D
ℓ=0 ℓ=1 ℓ=2
.. .. .. ..
. . . .
4S 1
n=4 2

3S 1
n=3 2 3P 3 3D 3
2 2
(2) (6) 3P 1 (10) 3D 5
2 2

2S 1
n=2 2 2P 3
2
(2) (6) 2P 1
2

1S 1
n=1 2

(2)

The number of states is indicated in parenthesis.

2.2 The Pauli equation

In the hydrogen atom the spin-orbit coupling arises because the electron is moving in the
electric field of the proton. Since the electron is moving relative to the frame where we have
a static electric field, the electron also sees a magnetic field B. The spin-orbit coupling is
the coupling −µ · B of that magnetic field to the magnetic dipole moment µ of the electron.
We have discussed before, in the context of the Stern-Gerlach experiment, the value of
the magnetic dipole moment of the electron. Recall the logic we used. In Gaussian units,
the classical magnetic moment of a planar current loop is given by µ = Ic a, where I is the
current and a is the area vector associated with the loop. From this one quickly derives
that for a uniformly rotating particle with charge q and mass m the magnetic moment is
q
µ= L, (2.2.1)
2mc
where L is the angular momentum due to the rotation. For an elementary particle, this
motivates the following relation between the spin angular momentum operator Ŝ and the
magnetic moment
q
µ = g Ŝ (2.2.2)
2mc
where g is a factor that is added to parameterize our ignorance; after all there is no reason
why the classically motivated formula for the magnetic dipole should hold in the quantum
domain of spin. As it turns out, for an electron one has g = 2. Since q = −e for an electron,
2.2. THE PAULI EQUATION 31

we have
−e e~ Ŝ e~ 1 e~
µ = 2 Ŝ = −2 = −2 2 σ = − σ. (2.2.3)
2me c 2me c ~ 2me c 2me c
For numerical applications we note that the Bohr magneton µB is defined by

e~ erg eV
µB = ≃ 9.274 × 10−21 = 5.79 × 10−9 . (2.2.4)
2me c gauss gauss

(for SI values use Tesla = 104 gauss). The coupling of an electron to an external magnetic
field is therefore represented by a Hamiltonian HB given by

e~
HB = −µ · B = σ · B. (2.2.5)
2me c

Our goal now is to show that this coupling, and its associated prediction of g = 2, arises
naturally from the non-relativistic Pauli equation for an electron.
Consider first the time-independent Schrödinger equation for a free particle:

p̂2
ψ = Eψ. (2.2.6)
2m
Since a spin one-half particle has two degrees of freedom, usually assembled into a column
vector χ, the expected equation for a free spin one-half particle is
 
p̂2 χ1
χ = E χ with χ = . (2.2.7)
2m χ2

One sometimes calls χ a Pauli spinor. Note there’s an implicit two-by-two identity matrix
12×2 in the Hamiltonian
p̂2
H = 12×2 . (2.2.8)
2m
We can rewrite this Hamiltonian using Pauli matrices if we recall the identity

(σ · a)(σ · b) = a · b 12×2 + iσ · (a × b) , (2.2.9)

valid for arbitrary vector operators a and b. Taking a = b = p̂, with p̂ the momentum
operator, and recognizing that p̂ × p̂ = 0, we have

(σ · p̂) · (σ · p̂) = p̂2 12×2 . (2.2.10)

This means that the Hamiltonian (2.2.8) can be rewritten as

1
H = (σ · p̂)(σ · p̂) . (2.2.11)
2m
32 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

So far, this is all just rewriting with no change in physics. But new things happen when we
the particle is charged and we couple it to external electromagnetic fields. The quantum
mechanical rule is that this inclusion can be taken care with the replacement
q
p̂ → π̂ ≡ p̂ − A. (2.2.12)
c

Here q is the charge of the particle and A is the external vector potential, a function
of position that becomes an operator A(x̂) since position is an operator. In addition, if
there is a electromagnetic scalar potential Φ it contributes an additional term qΦ(x̂) to the
Hamiltonian.
With the replacement (2.2.12) applied to the Hamiltonian (2.2.11), and the inclusion of
the coupling to the scalar potential, we get the Pauli Hamiltonian:

1
HPauli = (σ · π̂) (σ · π̂) + qΦ(x̂) . (2.2.13)
2m

This time, using the identity (2.2.9), the second term survives
1
HPauli = [(π̂ · π̂)1 + iσ · (π̂ × π̂)] + qΦ(x̂) . (2.2.14)
2m
We have π̂ × π̂ 6= 0 because the various πi do not commute. Note that the replacement
(2.2.12) applied to the original Hamiltonian (2.2.8) would not have given us the π̂ × π̂ term.
To evaluate that term we use
1
(π̂ × π̂)k = ǫijk π̂i π̂j = 2 ǫijk [π̂i , π̂j ] . (2.2.15)

The commutator here is

h q q i
[ πi , πj ] = pi − Ai , pj − Aj . (2.2.16)
c c
As usual, the p̂ components can be thought of as derivatives acting on the spatially de-
pendent components of A. Moreover, the Ai ’s being only functions of position, commute
among themselves and we have
~q i~q
[ πi , πj ] = − (∂i Aj − ∂j Ai ) = (∂i Aj − ∂j Ai ) . (2.2.17)
ic c
Therefore, back in (2.2.16)

1 i~q i~q i~q

(π × π)k = 2 ǫijk c (∂i Aj − ∂j Ai ) = ǫijk ∂i Aj = (∇ × A)k , (2.2.18)
c c
leading to the elegant result:
i~q
π̂ × π̂ = B. (2.2.19)
c
2.3. THE DIRAC EQUATION 33

This equation is a bit reminiscent of the equation L̂ × L̂ = i~L̂, for angular momentum.
Back in the Pauli Hamiltonian (2.2.14), leaving identity matrices implicit, and setting
q = −e, we find
1  e 2 i i~q
HPauli = p̂ + A + σ · B − eΦ(x̂)
2m c 2m c
(2.2.20)
1  e 2 e~
= p̂ + A + σ · B − eΦ(x̂) .
2m c 2mc
The second term in this expanded Pauli Hamiltonian gives the coupling of the electron spin
to the magnetic field and agrees precisely with the expected coupling (2.2.5). We thus see
that the Pauli equation predicts the g = 2 value in the electron magnetic moment.

2.3 The Dirac equation

While the Pauli equation incorporates correctly the coupling of the electron spin to electro-
magnetic fields, it is not a relativistic equation. As discovered by Dirac, to include relativity
one has to work with matrices and the Pauli spinor must be upgraded to a four-component
spinor. The analysis begins with the familiar relation between relativistic energies and
momenta p
E 2 − p2 c2 = m2 c4 → E = p2 c2 + m2 c4 (2.3.1)
This suggests that a relativistic Hamiltonian for a free particle could take the form
p
H = p̂2 c2 + m2 c4 , (2.3.2)

with associated Schrödinger equation

∂ψ p 2 2
i~ = p̂ c + m2 c4 ψ . (2.3.3)
∂t
It is not clear how to treat the square root so, at least for small velocities p ≪ mc, the
Hamiltonian can be expanded:
r "  2 2 #
2 p̂2 2 p̂2 1 p̂
H = mc 1 + 2 2 = mc 1 + − + ...
m c 2m2 c2 8 m2 c2
(2.3.4)
p̂2 1 p̂ 4
= mc2 + − + ...
2m 8 m3 c2
If we ignore the constant rest mass, the first term is the familiar non-relativistic Hamiltonian,
and the next term is the first nontrivial relativistic correction. For small momenta we will
treat that term as a perturbation.
More elegantly, Dirac wanted to find a Hamiltonian linear in momenta and without
square roots. This would be possible if one could write the relativistic energy as the square
of a linear function of the momentum:

c2 p̂2 + m2 c4 = (cα · p̂ + βmc2 )2 = (cα1 p̂1 + cα2 p̂2 + cα3 p̂3 + βmc2 )2 . (2.3.5)
34 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

Expanding the right-hand side and equating coefficients one finds that the following must
hold
α21 = α22 = α23 = β 2 = 1 ,
αi αj + αj αi = {αi , αj } = 0 , i 6= j , (2.3.6)
αi β + βαi = {αi , β} = 0 .
The relations on the second and third lines imply that α’s and β’s can’t be numbers, because
they would have to be zero. It turns out that α’s and β’s are four-by-four hermitian matrices:
   
0 σ 1 0
α= , β= . (2.3.7)
σ 0 0 −1
Using (2.3.5), the Dirac Hamiltonian is simply the linear function of momentum that is the
square root of c2 p̂2 + m2 c4 . We thus have

HDirac = cα · p + βmc2 . (2.3.8)

The Dirac equation is
∂Ψ

i~ = cα · p + βmc2 Ψ , (2.3.9)
∂t
where Ψ is a Dirac spinor, a four-component column vector that can be thought to be
composed by two two-component Pauli spinors χ and η:
     
χ χ1 η1
Ψ= , χ= , η= . (2.3.10)
η χ2 η2
The coupling to electromagnetic fields is done as before
∂Ψ h  e  i
i~ = cα · p̂ + A + βmc2 + V (r) Ψ , (2.3.11)
∂t c
where the coupling of the electron to the scalar potential Φ(r) is included via
e2
V (r) = −eΦ(r) = − . (2.3.12)
r
The great advantage of the Dirac equation (2.3.11) is that the corrections to the hydrogen
Hamiltonian H (0) can be derived systematically by finding the appropriate Hamiltonian H
that acts on the Pauli spinor χ. The analysis, can be done with A = 0, since the stationary
proton creates no vector potential. The result of the analysis shows that
Hχ = Eχ , (2.3.13)

where:

p̂2 p̂4 1 1 dV ~2
H = +V − 3 c2
+ 2 c2 r dr
S · L + 2 c2
∇2 V . (2.3.14)
2m
| {z } 8m
| {z } 2m
| {z } 8m
| {z }
H (0) δHrel. δHspin-orbit δHDarwin
2.4. FINE STRUCTURE OF HYDROGEN 35

The first correction is the relativistic energy correction anticipated earlier. The second is
the spin-orbit coupling, and the third is the Darwin correction, that as we shall see affects
only ℓ = 0 states.
Recall that the energy scale for H (0) eigenstates is α2 mc2 . We will now see that all the
1
above energy corrections are of order α4 mc2 thus smaller by a factor of α2 ≃ 19000 than the
zeroth-order energies. This suggests that for the hydrogen atom, the role of the unit-free
parameter λ of perturbation theory is taken by the fine structure constant: λ ∼ α2 . Of
course, in reality we cannot adjust the value of α2 nor we can take it to zero.
For the relativistic correction, recalling that p ≃ α mc, we indeed have
p4
δHrel. = − ∼ −α4 mc2 . (2.3.15)
8m3 c2
For spin-orbit we first rewrite the term, using
 2
1 dV 1 d e e2
= − = 3, (2.3.16)
r dr r dr r r
so that
e2 1
δHspin-orbit = S · L. (2.3.17)
2m2 c2 r 3
~ 1
For an estimate we set S · L ∼ ~2 , r ∼ a0 , and recall that a0 = mc α :

e2 ~2 α ~c ~2  ~ 3
δHspin-orbit ∼ = = α mc2 = α4 mc2 . (2.3.18)
m2 c2 a30 m2 c2 a30 mca0
We can evaluate the Darwin term using V = −e2 /r:
 
e2 ~2 1 e2 ~2 π e2 ~2
δHDarwin = − 2 2 ∇2 = 2 2
(−4πδ(r)) = δ(r) . (2.3.19)
8m c r 8m c 2 m2 c2
To estimate this correction note that, due to the δ function the the integral in the expecta-
tion value will introduce a factor |ψ(0)|2 ∼ a−3
0 . We will therefore have

e2 ~2
δHDarwin ∼ 2 2 3 ∼ α4 mc2 , (2.3.20)
m c a0
as this is exactly the same combination of constants that we had for spin orbit above.

2.4 Fine structure of hydrogen

The fine structure of hydrogen is the spectrum of the atom once one takes into account the
corrections indicated in (2.3.14). After the partial simplifications considered above we have
p̂2 p̂4 e2 S · L π e2 ~2
H = +V − 3 2
+ 2 2 3
+ 2 c2
δ(r) . (2.4.21)
|2m{z } |8m{zc } |2m c{z r } |2 m {z }
H (0) δHrel. δHspin-orbit δHDarwin
36 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

We will study each of these terms separately and then combine our results to give the fine
structure of hydrogen. There are further smaller corrections that we will not examine here,
such as hyperfine splitting and Lamb effect.

2.4.1 Darwin correction

Let us now evaluate the Darwin correction. Since this interaction has a delta function
at the origin, the first order correction to the energy vanishes unless the wavefunction is
non-zero at the origin. This can only happen for nS states. There is no need to use the
apparatus of degenerate perturbation theory. Indeed, for fixed n there are two orthogonal
ℓ = 0 states, one with electron spin up and one with electron spin down. While these states
are degenerate, the Darwin perturbation commutes with spin and is therefore diagonal in
the two-dimensional subspace. There is no need to include the spin in the calculation and
we have
(1) π e2 ~2
En00,Darwin = hψn00 |δHDarwin |ψn00 i = |ψn00 (0)|2 . (2.4.22)
2 m2 c2
As is shown in the homework, the radial equation can be used to determine the value of the
nS wavefunctions at the origin. You will find that
1
|ψn00 (0)|2 = . (2.4.23)
π n3 a30
As a result
(1) e2 ~2 1 1
En00,Darwin = 2 2 3 3
= α4 (mc2 ) 3 . (2.4.24)
2m c a0 n 2n
This completes the evaluation of the Darwin correction
The Darwin term in the Hamiltonian arises from the elimination of one of the two two-
component spinors in the Dirac equation. As we will show now such a correction would arise
from a nonlocal correction to the potential energy term. It is as if the electron had grown
from point-like to a ball with radius of order its Compton wavelength m~e c . The potential
energy due to the field of the proton must then be calculated by integrating the varying
electric potential over the charge distribution of the electron. While a simple estimate of
this nonlocal potential energy does reproduce the Darwin correction rather closely, one must
not reach the conclusion that the electron is no longer a point particle. Still the fact remains
that in a relativistic treatment of an electron, its Compton wavelength is relevant and is
physically the shortest distance an electron can be localized.
The potential energy V (r) of the electron, as a point particle, is the product of the
electron charge (−e) times the electric potential Φ(r) created by the proton:
e
V (r) = (−e)Φ(r) = (−e) . (2.4.25)
r
Let us call Ve (r) the potential energy when the electron is a charge distribution centered
at a point r with |r| = r (see Figure 2.1). This energy is obtained by integration over the
2.4. FINE STRUCTURE OF HYDROGEN 37

Figure 2.1: A Darwin type correction to the energy arises if the electron charge is smeared over a
region of size comparable to its Compton wavelength. Here the center of the spherically symmetric
electron cloud is at P and the proton is at the origin. The vector u is radial relative to the center
of the electron.

electron distribution. Using the vector u to define position relative to the center P of the
electron, and letting ρ(u) denote the position dependent charge density, we have
Z
e
V (r) = d3 u ρ(u)Φ(r + u) , (2.4.26)
electron

where, as shown in the Figure, r + u is the position of the integration point, measured
relative to the proton at the origin. It is convenient to write the charge density in terms of
a normalized function ρ0 :
Z
ρ(u) = −e ρ0 (u) → d3 u ρ0 (u) = 1 , (2.4.27)
electron

which guarantees that the integral of ρ over the electron is indeed (−e). Recalling that
−eΦ(r + u) = V (r + u) we now rewrite (2.4.26) as
Z
e
V (r) = d3 u ρ0 (u)V (r + u) . (2.4.28)
electron

This equation has a clear interpretation: the potential energy is obtained as a weighted
integral of potential due to the proton over the extended electron. If the electron charge
would be perfectly localized, ρ0 (u) = δ(u) and Ṽ (r) would just be equal to V (r). We will
assume that the distribution of charge is spherically symmetric, so that

ρ0 (u) = ρ0 (u) . (2.4.29)

38 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

To evaluate (2.4.31), we first do a Taylor expansion of the potential that enters the integral
about the point u = 0:
X 1X
V (r + u) = V (r) + ∂i V ui + ∂i ∂j V ui uj + . . . (2.4.30)
r 2 r
i i,j

All derivatives here are evaluated at the center of the electron. Plugging back into the
integral (2.4.31) and dropping the subscript ‘electron’ we have
Z  X 
e 1X
V (r) = d3 u ρ0 (u) V (r) + ∂i V ui + ∂i ∂j V ui uj + . . . . (2.4.31)
r 2 r
i i,j

All r dependent functions can be taken out of the integrals. Recalling that the integral of
ρ0 over volume is one, we get
X Z X Z
3
Ṽ (r) = V (r) + ∂i V 1
d u ρ0 (u) ρi + 2 ∂i ∂j V d3 u ρ0 (u) ui uj +. . . (2.4.32)
r r
i i,j

Due to spherical symmetry the first integral vanishes and the second takes the form
Z Z
d u ρ0 (u) ui uj = 3 δij d3 u ρ0 (u) u2 .
3 1
(2.4.33)

Indeed the integral must vanish for i 6= j and must take equal values for i = j = 1, 2, 3.
Since u2 = u21 + u22 + u23 , the result follows. Using this we get
X Z
Ṽ (r) = V (r) + 2 1
∂i ∂i V 3 d3 u f (u) ρ2 + . . .
1
r
i (2.4.34)
Z
1 2 3 2
= V (r) + 6∇ V d u ρ0 (u) u + . . . .

The second term represents the correction δV to the potential energy:

Z
1 2
δV = 6 ∇ V d3 u ρ0 (u) u2 . (2.4.35)

To get an estimate, let us assume that the charge is distributed uniformly over a sphere of
radius u0 . This means that ρ0 (u) is a constant for u < u0

3  1, u < u0 ,
ρ0 (u) = 3 (2.4.36)
4πu0  0, u>u . 0

The integral one must evaluate then gives

Z Z u0 Z u0
3 2 4πu2 du u2 3
d u ρ0 (u)u = 4π 3 = 3 u4 du = 35 u20 . (2.4.37)
0 u
3 0
u 0 0
2.4. FINE STRUCTURE OF HYDROGEN 39

Therefore,
1 2 2
δV = 10 u0 ∇ V . (2.4.38)
~
If we choose the radius u0 of the charge distribution to be the Compton wavelength mc of
the electron we get,
~2
δV = ∇2 V . (2.4.39)
10 m2 c2
Comparing with (2.3.14) we see that, up to a small correction ( 18 as opposed to 10
1
), this
is the Darwin energy shift. The agreement is surprisingly good for what is, admittedly, a
heuristic argument.

2.4.2 Relativistic correction

We now turn to the relativistic correction. The energy shifts of the hydrogen states can
be analyzed among the degenerate states with principal quantum number n. We write
tentatively for the corrections
(1) 1
En,ℓmℓ ms ;rel = − hψnℓmℓ ms |p2 p2 |ψnℓmℓ i . (2.4.40)
8m3 c2
We can use this formula because the uncoupled basis of states at fixed n is good: the
perturbation is diagonal in this basis. This is checked using Remark 3 in section 1.2.2. This
is clear because the perturbing operator p2 p2 commutes with L2 , with Lz , and with Sz .
The first operator guarantees that that the matrix for the perturbation is diagonal in ℓ, the
second guarantees that the perturbation is diagonal in mℓ , and the third guarantees, rather
trivially, that the perturbation is diagonal in ms .
To evaluate the matrix element we use the Hermiticity of p2 to move one of the factors
into the bra
(1) 1
En,ℓmℓ ms ;rel = − 3 2 hp2 ψnℓm |p2 ψnℓm i , (2.4.41)
8m c
where in the right-hand side we evaluated the trivial expectation value for the spin degrees
of freedom. To simplify the evaluation we use the Schrödinger equation, which tells us that
 p2 
+ V ψnℓm = En(0) ψnℓm → p2 ψnℓm = 2m(En(0) − V )ψnℓm . (2.4.42)
2m
Using this both for the bra and the ket:
(1) 1 D (0) (0)
E
En,ℓmℓ ms ;rel = − (E n − V )ψnℓm (En − V )ψnℓm . (2.4.43)
2mc2
(0)
The operator En − V is also Hermitian and can be moved from the bra to the ket, giving
(1) 1 D (0) 2 (0) 2
E
En,ℓmℓ ms ;rel = − ψnℓm ( (En ) − 2V En + V ) ψ nℓm
2mc2
(2.4.44)
1 h (0) 2 2
i
= − (En ) − 2En hV inℓm + hV inℓm .
2mc2
40 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

The problem has been reduced to the computation of the expectation value of V (r) and
V 2 (r) in the ψnℓm state. The expectation value of V (r) is obtained from the virial theorem
(0)
that states that hV i = 2En . For V 2 (r) we have

D1E  2 2
1 e 1 4n 4n
hV 2 i = e4 = e4
1

= (0) 2
1 = (En ) · . (2.4.45)
r2 2 3
a0 n ℓ + 2 2a 0 n 2 ℓ+ 2 ℓ + 21

Back into (2.4.44) we find

(En )2 h 4n i 2 h 4n i
(0)
(1) 1 4 (mc )
En,ℓmℓ ms ;rel = − − 3 = − 8 α − 3 . (2.4.46)
2mc2 ℓ + 12 n4 ℓ + 21

The complete degeneracy of ℓ multiplets for a given n has been broken. That degeneracy
of H (0) was explained by the conserved Runge-Lenz vector. It is clear that the relativistic
correction has broken that symmetry.
We have computed the above correction using the uncoupled basis

(1)
En,ℓmℓ ms ;rel = hnℓmms |δHrel |nℓmms i = f (n, ℓ) . (2.4.47)

Here we added the extra equality to emphasize that the matrix elements depend only on n
and ℓ. We have already seen that in the full degenerate subspace with principal quantum
number n the matrix for δHrel is diagonal in the uncoupled basis. But now we see that in
each degenerate subspace of fixed n and ℓ, δHrel is in fact a multiple of the identity matrix,
since the matrix elements are independent of m and ms (the Lz and Sz ) eigenvalues. A
matrix equal to a multiple of the identity is invariant under any orthonormal change of
basis. For any ℓ ⊗ 12 multiplet, the resulting j multiplets provide an alternative orthonormal
basis. The invariance of a matrix proportional to the identity implies that

(1)
Enℓjmj ,rel = hnℓjmj |δHrel |nℓjmj i = f (n, ℓ) . (2.4.48)

with the same function f (n, ℓ) as in (2.4.47), and the perturbation is diagonal in this coupled
basis too. This is clear anyway because the perturbation commutes with L2 , J2 and Jz and
and any two degenerate states in the coupled basis differ either in ℓ, j or jz .
The preservation of the matrix elements can also be argued more explicitly. Indeed,
any state in the coupled basis is a superposition of orthonormal uncoupled basis states with
constant coefficients ci :
X X
|nℓjmj i = ci |nℓmiℓ mis i , with |ci |2 = 1 , (2.4.49)
i i

because the state on the left-hand side must also have unit norm. Therefore, using the
2.4. FINE STRUCTURE OF HYDROGEN 41

diagonal nature of the matrix elements in the uncoupled basis we get, as claimed
X
hnℓjmj |δHrel |nℓjmj i = c∗i ck hnℓmiℓ mis |δHrel |nℓmkℓ mks i
i,k
X
= |ci |2 hnℓmiℓ mis |δHrel |nℓmiℓ mis i (2.4.50)
i
X
= |ci |2 f (n, ℓ) = f (n, ℓ) .
i

2.4.3 Spin orbit coupling

The spin-orbit contribution to the Hamiltonian is

e2 1
δHspin-orbit = S · L. (2.4.51)
2m2 c2 r 3

Note that δHspin-orbit commutes with L2 because L2 commutes with any L̂i and any Ŝi .
Moreover, δHspin-orbit commutes with J2 and with Jz since, in fact, [Jˆi , S · L] = 0 for
any i; S · L is a scalar operator for J. It follows that δHspin-orbit is diagonal in the level
n degenerate subspace in the coupled basis |nℓjmj i. In fact, as we will see, the matrix
elements are m-independent. This is a nontrivial consequence of δHspin-orbit being a scalar
under J. To compute the matrix elements we recall that J = S + L and

(1) e2 D 1 E
Enℓjmj ; spin-orbit = nℓjm j 3 S · L nℓjm j
2m2 c2 r
e2 ~2  3
D 1 E
= j(j + 1) − ℓ(ℓ + 1) − 4 nℓjm j 3 nℓjm j . (2.4.52)
2m2 c2 2 r
We need the expectation value of 1/r 3 in these states. It is known that
D 1 E 1
nℓmℓ nℓm ℓ = 3 3
. (2.4.53)
r 3 n a0 ℓ ℓ + 12 (ℓ + 1)

Because of the mℓ independence of this expectation value (and its obvious ms independence)
the operator 1/r 3 is a multiple of the identity matrix in each ℓ ⊗ 12 multiplet. It follows that
it is the same multiple of the identity in the coupled basis description. Therefore
D 1 E 1
nℓjmj 3 nℓjmj = 3 3
. (2.4.54)
r n a0 ℓ ℓ + 12 (ℓ + 1)

Using this in (2.4.52)

 
(1) e2 ~2 j(j + 1) − ℓ(ℓ + 1) − 34
Enℓjmj ; spin-orbit =
. (2.4.55)
4m2 c2 n3 a30 ℓ ℓ + 12 (ℓ + 1)
42 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

(0)
Working out the constants in terms of En and rest energies we get
(0)  
(1) (En )2 n j(j + 1) − ℓ(ℓ + 1) − 34
Enℓjmj ; spin-orbit =
, ℓ 6= 0 . (2.4.56)
mc2 ℓ ℓ + 21 (ℓ + 1)

Since L vanishes identically acting on any ℓ = 0 state, it is physically reasonable, as we will

do, to assume that the spin-orbit correction vanishes for ℓ = 0 states. On the other hand
the limit of the above formula as ℓ → 0, while somewhat ambiguous, is nonzero. We set
j = ℓ + 21 (the other possibility j = ℓ − 12 does not apply for ℓ = 0) and then take the limit
as ℓ → 0. Indeed,
(0)  
(1) (En )2 n (ℓ + 21 )(ℓ + 32 ) − ℓ(ℓ + 1) − 34
Enℓjmj ; spin-orbit =

j=ℓ+ 21 mc2 ℓ ℓ + 21 (ℓ + 1)
(0)
(2.4.57)
(En )2 n
=
,
mc2 ℓ + 12 (ℓ + 1)

and now taking the limit:

(0)
(1) (En )2 1
lim Enℓjmj ; spin-orbit = 2
(2n) = α4 mc2 3 . (2.4.58)
ℓ→0 j=ℓ+ 21 mc 2n

We see that this limit is in fact identical to the Darwin shift (2.4.24) of the nS states. This
is a bit surprising and will play a technical role below.

2.4.4 Combining results

For ℓ 6= 0 states we can add the energy shifts from spin-orbit and from the relativistic
correction, both of them expressed as expectation values in the coupled basis. The result,
therefore will give the shifts of the coupled states. Collecting our results (2.4.46) and (2.4.56)
we have
D E
nℓjmj δHrel + δHspin-orbit nℓjmj
(  )
(0)
(En )2 4n 2n j(j + 1) − ℓ(ℓ + 1) − 34
= 3−
+

2mc2 ℓ + 21 ℓ ℓ + 12 (ℓ + 1) (2.4.59)
( " #)
(0)
(En )2 j(j + 1) − 3ℓ(ℓ + 1) − 43
= 3 + 2n
.
2mc2 ℓ ℓ + 21 (ℓ + 1)

These are the fine structure energy shifts for all states in the spectrum of hydrogen. The
states in a coupled multiplet are characterized by ℓ, j and mj and each multiplet as a whole
is shifted according to the above formula. The degeneracy within the multiplet is unbroken
because the formula has no mj dependence. This formula, as written, hides some additional
degeneracies. We uncover those next.
2.4. FINE STRUCTURE OF HYDROGEN 43

In the above formula there are two cases to consider for any fixed value of j: the multiplet
can have ℓ = j − 12 or the multiplet can have ℓ = j + 21 . We will now see something rather
surprising. In both of these cases the shift is the same, meaning that the shift is in fact ℓ
independent! It just depends on j. Call f (j, ℓ) the term in brackets above
3
j(j + 1) − 3ℓ(ℓ + 1) − 4
f (j, ℓ) ≡
. (2.4.60)
ℓ ℓ + 21 (ℓ + 1)

The evaluation of this expression in both cases gives the same result:

j(j + 1) − 3(j − 12 )(j + 12 ) − 3

4 −2j 2 + j 2
f (j, ℓ) =

=


1 =−

,
ℓ=j− 21 j − 12 j j + 21 1
j j−2 j+2 j + 12

j(j + 1) − 3(j + 12 )(j + 32 ) − 3

4 2j 2 − 5j − 3 2
f (j, ℓ) =

=


3 =−

.
ℓ=j+ 21 j + 21 (j + 1) j + 32 1
j + 2 (j + 1) j + 2 j + 12
(2.4.61)

We can therefore replace in (2.4.59) the result of our evaluation, which we label as fine
structure (fs) shifts:

(En )2 h 4n i h n i
(0)
(1) 4 2 1 3
Enℓj,mj ;fs = − − 3 = −α (mc ) − 4 . (2.4.62)
2mc2 j + 12 2n4 j + 1
2

More briefly we can write

(1) 1 h n i
Enℓj,mj ;fine = −α4 mc2 · Sn,j , with Sn,j ≡ 1 − 3
4 . (2.4.63)
2n4 j + 2

Let us consider a few remarks:

1. The dependence on j and absence of dependence on ℓ in the energy shifts could be

anticipated from the Dirac equation. The rotation generator that commutes with the
Dirac Hamiltonian is J = L + S, which simultaneously rotates position, momenta, and
spin states. Neither L nor S are separately conserved. With J a symmetry, states are
expected to be labelled by energy and j and must be mj independent.

2. The formula (2.4.63) works for nS states! For these ℓ = 0 states we were supposed
to add the relativistic correction and the Darwin correction, since their spin-orbit
correction is zero. But we noticed that the limit ℓ → 0 of the spin-orbit correction
reproduces the Darwin term. Whether or not this is a meaningful coincidence, it
means the sum performed above gives the right answer for ℓ → 0.

3. While a large amount of the degeneracy of H (0) has been broken, for fixed n, multiplets
with the same value of j, regardless of ℓ, remain degenerate. The states in each j
multiplet do not split.
44 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

4. Since Sn,j > 0 all energy shifts are down. Indeed

n n n n n 3 1
1 ≥ 1 = = =1 → − 4 ≥ 4 . (2.4.64)
j+ 2 jmax + 2 ℓmax + 12 + 1
2
n j+ 1
2

5. For a given fixed n, states with lower values of j get pushed further down. As n
increases splittings fall off like n−3 .

A table of values of Sn,j is given here below

n j Sn,j
1 1
1 2 8
1 5
2 2 128
3 1
2 128
1 1
3 2 72
3 1
2 216
5 1
2 648

The energy diagram for states up to n = 3 is given here (not to scale)

S P D
ℓ=0 ℓ=1 ℓ=2
.. .. .. ..
. . . .
n=3
3D5/2
3P3/2 3D3/2
3S1/2 3P1/2

n=2 Fine Structure Spectrum

2P3/2
2S1/2 2P1/2

n=1

1S1/2
2.5. ZEEMAN EFFECT 45

For the record, the total energy of the hydrogen states is the zeroth contribution plus
the fine structure contribution. Together they give

e2 1 h α2  n 3
i
Enℓjmj = − 1 + 1 − 4 . (2.4.65)
2a0 n2 n2 j + 2

This is the fine structure of hydrogen! There are, of course, finer corrections. The so-
called Lamb shift, for example, breaks the degeneracy between 2S1/2 and 2P1/2 and is of
order α5 . There is also hyperfine splitting, which arises from the coupling of the magnetic
moment of the proton to the magnetic moment of the electron. Such coupling leads to a
splitting that is a factor me /mp smaller than fine structure.

2.5 Zeeman effect

In remarkable experiment done in 1896, the Dutch physicist Pieter Zeeman (1865-1943)
discovered that atomic spectral lines are split in the presence of an external magnetic field.
For this work Zeeman was awarded the Nobel Prize in 1902. The proper understanding of
this phenomenon had to wait for Quantum Mechanics.
The splitting of atomic energy levels by a constant, uniform, external magnetic field, the
Zeeman effect, has been used as a tool to measure inaccessible magnetic fields. In observing
the solar spectrum, a single atomic line, as seen from light emerging from outside a sunspot,
splits into various lines inside the sunspot. We have learned that magnetic fields inside a
sunspot typically reach 3, 000 gauss. Sunspots are a bit darker and have lower temperature
than the rest of the solar surface. They can last from hours to months, and their magnetic
energy can turn into powerful solar flares.
The external magnetic field interacts with the total magnetic moment of the electron.
The electron has magnetic moment due to its orbital angular momentum and one due to
its spin
e e
µℓ = − L , µs = − S, (2.5.1)
2mc mc
where we included the g = 2 factor in the spin contribution. The Zeeman Hamiltonian is
thus given by
e
δHZeeman = −(µℓ + µs ) · B = (L + 2S) · B . (2.5.2)
2mc
Conventionally, we align the magnetic field with the positive z axis so that B = B z and
thus get
eB
δHZeeman = (L̂z + 2Ŝz ) . (2.5.3)
2mc
When we consider the Zeeman effect on Hydrogen we must not forget fine structure.
The full Hamiltonian to be considered is

H = H (0) + δHfs + δHZeeman . (2.5.4)

46 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

Recall that in fine structure, there is an internal magnetic field Bint associated with spin-
orbit coupling. This is the magnetic field seen by the electron as it goes around the proton.
We have therefore two extreme possibilities concerning the external magnetic field B of the
Zeeman effect:

(1) Weak-field Zeeman effect: B ≪ Bint . In this case the Zeeman effect is small compared
with fine structure effects. Accordingly, the original Hamiltonian H (0) together with
the fine structure Hamiltonian Hfs are thought as the “known” Hamiltonian H̃ (0) , and
the Zeeman Hamiltonian is the perturbation:

H = H (0) + δHfs +δHZeeman . (2.5.5)

| {z }
H̃ (0)

(2) Strong-field Zeeman effect: B ≫ Bint . In this case the Zeeman effect is much larger
than fine structure effects. Accordingly, the original Hamiltonian H (0) together with
the Zeeman Hamiltonian are thought as the “known” Hamiltonian Ȟ (0) and the fine
structure Hamiltonian Hfs is viewed as the perturbation:

H = H (0) + δHZeeman +δHfs . (2.5.6)

| {z }
Ȟ (0)

You may thing that H (0) + δHZeeman does not qualify as known, but happily, as we
will confirm soon, this is actually a very simple Hamiltonian.

When the Zeeman magnetic field is neither weak nor strong, we must take the sum
of the Zeeman and fine structure Hamiltonians as the perturbation. No simplification is
possible and one must diagonalize the perturbation.
Weak-field Zeeman effect. The approximate eigenstates of H̃ (0) are the coupled states
|nℓjmj i that exhibit fine structure corrections and whose energies are a function of n and j,
as shown in the Fine Structure diagram. Degeneracies in this spectrum occur for different
values of ℓ and different values of mj .
To figure out the effect of the Zeeman interaction on this spectrum we consider the
matrix elements:
hnℓjmj |δHZeeman |nℓ′ jm′j i . (2.5.7)

Since δHZeeman ∼ Lz + 2Sz we see that δHZeeman commutes with L2 and with Jˆz . The
matrix element thus vanishes unless ℓ′ = ℓ and m′j = mj and the Zeeman perturbation is
diagonal in the degenerate fine structure eigenspaces. The energy corrections are therefore

(1) e~ 1
Enℓjmj = B hnℓjmj |(L̂z + 2Ŝz )|nℓjmj i , (2.5.8)
2mc ~
where we multiplied and divided by ~ to make the units of the result manifest. The result
of the evaluation of the matrix element will show a remarkable feature: a linear dependence
2.5. ZEEMAN EFFECT 47

E (1) ∼ ~mj on the azimuthal quantum numbers. The states in each j multiplet split into
equally separated energy levels! We will try to understand this result as a property of
matrix elements of vector operators. First, however, note that L̂z + 2Ŝz = Jˆz + Ŝz and
therefore the matrix element of interest in the above equation satisfies
hnℓjmj |(L̂z + 2Ŝz )|nℓjmj i = ~m + hnℓjmj |Ŝz |nℓjmj i . (2.5.9)
It follows that we only need to concern ourselves with Ŝz matrix elements.
Let’s talk about vector operators. The operator V̂ is said to be a vector operator
under an angular momentum operator Ĵ if the following commutator holds for all values of
i, j = 1, 2, 3:  
Jˆi , V̂j = i~ ǫijk V̂k . (2.5.10)
It follows from the familiar Ĵ commutators that Ĵ is a vector operator under Ĵ. Additionally,
if V̂ is a vector operator it has a standard commutation relation with Ĵ2 that can be quickly
confirmed:

[Ĵ2 , V̂] = 2i~ V̂ × Ĵ − i~ V̂ . (2.5.11)
If V̂ is chosen to be Ĵ the left-hand side vanishes by the standard property of Ĵ2 and the
right-hand side vanishes because the Ĵ commutation relations can be written as Ĵ× Ĵ = i~Ĵ.
Finally, by repeated use of the above identities you will show (homework) that the following
formula holds
1 h 2 i

2
Ĵ , [Ĵ 2
, V̂] = (V̂ · Ĵ) Ĵ − 12 Jˆ2 V̂ + V̂ Jˆ2 . (2.5.12)
(2i~)
Consider (Ĵ2 , Jˆz ) eigenstates |k; jmj i where k stands for other quantum number that bear
no relation to angular momentum. The matrix elements of the left-hand side of (2.5.12) on
such eigenstates is necessarily zero:
h i
hk′ ; jm′j | Ĵ2 , [Ĵ2 , V̂] |k; jmj i = 0 , (2.5.13)

as can be seen by expanding the outer commutator and noticing that Ĵ2 gives the same
eigenvalue when acting on the bra and on the ket. Therefore the matrix elements of the
right-hand side gives
hk′ ; jm′j |(V̂ · Ĵ) Ĵ|k; jmj i = ~2 j(j + 1) hk′ ; jm′j |V̂|k; jmj i , (2.5.14)
which implies that

′
hk′ ; jm′j |(V̂ · Ĵ) Ĵ|k; jmj i
hk ; jm′j |V̂|k; jmj i = . (2.5.15)
~2 j(j + 1)

This is the main identity we wanted to establish. Using the less explicit notation h· · · i for
the matrix elements we have found that
h(V̂ · Ĵ) Ĵ i
hV̂i = . (2.5.16)
hĴ2 i
48 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

This is sometimes called the projection lemma: the matrix elements of a vector operator V̂
are those of the conventional projection of V̂ onto Ĵ. Recall that the projection of a vector
v along the vector j is (v · j)j/j2 .
Let us now return to the question of interest; the computation of the the expectation
value of Ŝz in (2.5.20). Since Ŝ is a vector operator under Ĵ we can use (2.5.15). Specializing
to the z-component

~mj hnℓ jmj |Ŝ · Ĵ |nℓ jmj i

hnℓ jmj |Ŝz |nℓ jmj i = . (2.5.17)
~2 j(j + 1)
We already see the appearance of the predicted ~mj factor. The matrix element in the
numerator is still to be calculated but it will introduce no mj dependence. In fact Ŝ · Ĵ is a
scalar operator (it commutes with all Jˆi ) and therefore it is diagonal in mj . But even more
is true; the expectation value of a scalar operator is in fact independent of mj ! We will not
show this here, but will just confirm it by direct computation. Since L̂ = Ĵ − Ŝ we have


Ŝ · Ĵ = 12 Ĵ2 + Ŝ2 − L̂2 , (2.5.18)

and therefore
~mj

hnℓ jmj |Ŝz |nℓ jmj i = j(j + 1) − ℓ(ℓ + 1) + 43 . (2.5.19)
2j(j + 1)
Indeed, no further mj dependence has appeared. Back now to (2.5.20) we get
 j(j + 1) − ℓ(ℓ + 1) + 34 
hnℓjmj |(L̂z + 2Ŝz )|nℓjmj i = ~mj 1 + . (2.5.20)
2j(j + 1)
The constant of proportionality in parenthesis is called the Lande g-factor gJ (ℓ):
3
j(j + 1) − ℓ(ℓ + 1) + 4
gJ (ℓ) ≡ 1 + (2.5.21)
2j(j + 1)
We finally have for the Zeeman energy shifts in (2.5.8)

(1) e~
Enℓjmj = B gJ (ℓ) mj . (2.5.22)
2mc
e~
Here the Bohr magneton 2mc ≃ 5.79 × 10−9 eV/gauss. This is our final result for the weak-
field Zeeman energy corrections to the fine structure energy levels. Since all degeneracies
within j multiplets are broken and j multiplets with different ℓ split differently due to the
ℓ dependence of gJ (ℓ), the weak-field Zeeman effect removes all degeneracies!
Strong-field Zeeman effect. We mentioned earlier that when the Zeeman effect is larger
than the fine structure corrections we must take the original hydrogen Hamiltonian together
with the Zeeman Hamiltonian to form the ‘known’ Hamiltonian Ȟ (0) :
e
Ȟ (0) = H (0) + (L̂z + 2Ŝz )B . (2.5.23)
2mc
2.5. ZEEMAN EFFECT 49

Actually Ȟ (0) is simple because the Zeeman Hamiltonian commutes with the zero-th order
hydrogen Hamiltonian  
L̂z + 2Ŝz , H (0) = 0 . (2.5.24)
We can thus find eigenstates of both simultaneously. Those are in fact the uncoupled basis
states! We have
H (0) |nℓmℓ ms i = En(0) |nℓmℓ ms i
(2.5.25)
(L̂z + 2Ŝz )|nℓmℓ ms i = ~(mℓ + 2ms )|nℓmℓ ms i .

and therefore the uncoupled basis states are the exact energy eigenstates of Ȟ (0) and have
energies
e~
Enℓmℓ ms = En(0) + B(mℓ + 2ms ) . (2.5.26)
2mc
Some of the degeneracy of H (0) has been removed, but some remains. For a fixed principal
quantum number n there are degeneracies among ℓ ⊗ 21 states and degeneracies among such
multiplets with ℓ and ℓ′ different. This is illustrated in Figure 2.2.

Figure 2.2: Illustrating the degeneracies remaining for ℓ = 0 and ℓ = 1 after the inclusion of Zeeman
term in the Hamiltonian. Accounting for the spin of the electron there two degenerate states in the
ℓ = 1 multiplet 1 ⊗ 21 and each of the two states in the ℓ = 0 multiplet 0 ⊗ 12 is degenerate with a
state in the ℓ = 1 multiplet.

The problem now is to compute the corrections due to δHfs on the non-degenerate and
on the degenerate subspaces of Ȟ (0) . The non-degenerate cases are straightforward, but
the degenerate cases could involve diagonalization. We must therefore consider the matrix
elements
hnℓ′ m′ℓ m′s | δHfs |nℓmℓ ms i , (2.5.27)
with the condition
m′ℓ + 2m′s = mℓ + 2ms , (2.5.28)
50 CHAPTER 2. HYDROGEN ATOM FINE STRUCTURE

needed for the two states in the matrix element to belong to a degenerate subspace. Since
L̂2 commutes with δHfs the matrix elements vanish unless ℓ = ℓ′ and therefore it suffices to
consider the matrix elements

hnℓ′ m′ℓ m′s | δHfs |nℓmℓ ms i , (2.5.29)

still with condition (2.5.28). Ignoring ℓ = 0 states, we have to re-examine the relativistic
correction and spin orbit. The relativistic correction was computed in the uncoupled basis
and one can use the result because the states are unchanged and the perturbation was
shown to be diagonal in this basis. For spin-orbit the calculation was done in the coupled
basis because spin-orbit is not diagonal in the original H (0) degenerate spaces using the
uncoupled basis. But happily, it turns out that spin-orbit is diagonal in the more limited
degenerate subspaces obtained after the Zeeman effect is included. All these matters are
explored in the homework.
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8.06 Quantum Physics III

Spring 2018

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Chapter 3

Semiclassical approximation

c B. Zwiebach

3.1 The classical limit

The WKB approximation provides approximate solutions for linear differential equations
with coefficients that have slow spatial variation. The acronym WKB stands for Wentzel,
Kramers, Brillouin, who independently discovered it in 1926. It was in fact discovered
earlier, in 1923 by the mathematician Jeffreys. When applied to quantum mechanics, it is
called the semi-classical approximation, since classical physics then illuminates the main
features of the quantum wavefunction.
The de Broglie wavelength λ of a particle can help us assess if classical physics is relevant
to the physical situation. For a particle with momentum p we have

h
λ= . (3.1.1)
p

Classical physics provides useful physical insight when λ is much smaller than the relevant
length scale in the problem we are investigating. Alternatively if we take h → 0 this will
formally make λ → 0, or λ smaller than the length scale of the problem. Being a constant of
nature, we cannot really make ~ → 0, so taking this limit is a thought experiment in which
we imagine worlds in which h takes smaller and smaller values making classical physics more
and more applicable. The semi-classical approximation studied here will be applicable if
a suitable generalization of the de Broglie wavelength discussed below is small and slowly
varying. The semi-classical approximation will be set up mathematically by thinking of ~
as a parameter that can be taken to be as small as desired.

Our discussion in this chapter will focus on one-dimensional problems. Consider there-
fore a particle of mass m and total energy E moving in a potential V (x). In classical physics
E − V (x) is the kinetic energy of the particle at x. This kinetic energy depends on position.

51
52 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

p2
Since kinetic energy is 2m this suggests the definition of the local momentum p(x):

p2 (x) ≡ 2m(E − V (x)) . (3.1.2)

The local momentum p(x) is the momentum of the classical particle when it is located at
x. With a notion of local momentum, we can define a local de Broglie wavelength λ(x)
by the familiar relation:
h 2π~
λ(x) ≡ = . (3.1.3)
p(x) p(x)
The time-independent Schrödinger equation

~2 ∂ 2
− ψ(x) = (E − V (x))ψ(x) . (3.1.4)
2m ∂x2
can be written nicely in terms of the local momentum squared :

∂2
−~2 ψ = p2 (x) ψ . (3.1.5)
∂x2
Using the momentum operator, this equation takes the suggestive form

p̂2 ψ(x) = p2 (x) ψ(x) . (3.1.6)

This has the flavor of an eigenvalue equation but it is not one: the action of the momentum
operator squared on the wavefunction is not really proportional to the wavefunction, it is
the wavefunction multiplied by the ‘classical’ position-dependent momentum-squared.
A bit of extra notation is useful. If we are in the classically allowed region, E > V (x)
and p2 (x) is positive. We then write

p2 (x) = 2m(E − V (x)) = ~2 k 2 (x) , (3.1.7)

introducing the local, real wavenumber k(x). If we are in the classically forbidden region,
V (x) > E and p2 (x) is negative. We then write

−p2 (x) = 2m(V (x) − E) = ~2 κ2 (x) , (3.1.8)

introducing the local, real κ(x).

The wavefunctions we use in the WKB approximation are often expressed in polar form.
Just like any complex number z can be written as reiθ , where r and θ are the magnitude
and phase of z, respectively, we can write the wavefunction in a similar way:
p i 
Ψ(x, t) = ρ(x, t) exp S(x, t) . (3.1.9)
~
3.2. WKB APPROXIMATION SCHEME 53

We are using here three-dimensional notation for generality. By definition, the functions
ρ(x, t) and S(x, t) are real. The function ρ is non-negative and the function S(x, t) as
written, has units of ~. The name ρ(x, t) is well motivated, for it is in fact the probability
density:
ρ(x, t) = |Ψ(x, t)|2 . (3.1.10)
Let’s compute the probability current. For this we begin by taking the gradient of the
wavefunction
1 ∇ρ iS i
∇Ψ = √ e ~ + ∇S Ψ (3.1.11)
2 ρ ~
We then form:
1 i
Ψ∗ ∇Ψ = ∇ρ + ρ∇S (3.1.12)
2 ~
The current is given by
~
J= Im (Ψ∗ ∇Ψ) . (3.1.13)
m
It follows that
∇S
J = ρ . (3.1.14)
m

This formula implies that the probability current J is perpendicular to the surfaces of
constant S, the surfaces of constant phase in the wavefunction.
In classical physics a fluid with density ρ(x) moving with velocity v(x) has a current
p
density ρv = ρ m . Comparing with the above expression for the quantum probability
current, we deduce that
p(x) ' ∇S . (3.1.15)
We use the ' because this is an association that is not of general validity. Nevertheless,
for ‘basic’ WKB solutions we will see that the gradient of S is indeed the classical local
momentum! This association also holds for a free particle:
Example. Consider a free particle with momentum p and energy E. Its wavefunction is
 
ip · x iEt
Ψ(x, t) = exp − . (3.1.16)
~ ~

Here we identify the function S as S = p · x − Et and therefore ∇S = p. In this case ∇S

is equal to the momentum eigenvalue, a constant.

3.2 WKB approximation scheme

Our aim here is to find approximate solutions for the wavefunction ψ(x) that solves the
time independent Schrd̈inger equation in one dimension. We wrote before the polar decom-
position (3.1.9) of the wavefunction. It will be easier to set the approximation scheme by
54 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

using a single complex function S(x) to represent the time-independent wavefunction ψ(x).
For this we use a pure exponential without any prefactor:
i 
ψ(x) = exp S(x) , S(x) ∈ C . (3.2.1)
~
As before S must have units of ~. This S(x) here is a complex number, because wavefunc-
tions are not in general pure phases. The real part of S, divided by ~, is the phase of the
wavefunction. The imaginary part of S(x) determines the magnitude of the wavefunction.
Let us plug this into the Schrödinger equation (3.1.5):

d2  i S(x)  i
−~2 2
e~ = p2 (x)e ~ S(x) . (3.2.2)
dx
Let us examine the left-hand side and take the two derivatives
 00
2  i (S 0 )2
  
2 d d i 0 iS
 i i
S(x) 2 S(x) 2
−~ 2
e~ = −~ S (x)e ~ = −~ − 2 e ~ S(x) . (3.2.3)
dx dx ~ ~ ~

Back into the differential equation and canceling the common exponential
 00
(S 0 )2

iS
−~2 − 2 = p2 (x) . (3.2.4)
~ ~

With minor rearrangements we get our final form:

(S 0 (x))2 − i~S 00 (x) = p2 (x) . (3.2.5)

The presence of an explicit iin the equation tells us that the solution for S, as expected,
cannot be real. At first sight one may be baffled: we started with the linear Schrödinger
equation for ψ and obtained a nonlinear equation for S! This is actually unavoidable when
the variable ψ is parameterized as an exponential and reminds us that sometimes a change
of variables can turn a linear equation into a nonlinear one and viceversa. The nonlinear
equation (3.2.5) allows us set up an approximation scheme in which ~ is considered small
and thus the term involving S 00 (x) is small. We will argue that this is in fact true for slowly
varying potentials.
Claim: i~S 00 small if V (x) is slowly varying.
Indeed, if V (x) = V0 is a constant, then the local momentum p(x) is equal to a constant p0 .
Equation (3.2.5) is then solved by taking S 0 = p0 . For this choice S 00 = 0 and the term i~S 00
vanishes identically for constant V . It should therefore be small for slowly varying V (x).
Alternatively the term i~S 00 in the differential equation is small as ~ → 0, which makes
the local de Broglie wavelength go to zero. In that case, the potential looks constant to the
quantum particle.
3.2. WKB APPROXIMATION SCHEME 55

We will thus take ~ to be the small parameter in a systematic expansion of S(x):

S(x) = S0 (x) + ~S1 (x) + ~2 S2 (x) + O(~3 ) . (3.2.6)

Here S0 , just like S, has units of ~. The next correction S1 has no units, and the following,
S2 has units of one over ~. Now plug this expansion into our nonlinear equation (3.2.5)

2
S00 + ~S10 + ~2 S20 + . . . − i~ S000 + ~S100 + ~2 S200 + . . . − p2 (x) = 0 .


(3.2.7)

The left-hand side is a power series expansion in ~. Just as we argued for the parameter λ
in perturbation theory, here we want the left-hand side to vanish for all values of ~ and this
requires that the coefficient of each power of ~ vanishes. We thus sort the left-hand side
terms neglecting terms of order ~2 or higher. We find

(S00 )2 − p2 + ~ 2S00 S10 − iS000 + O ~2 = 0

(3.2.8)

This gives two equations, one for the coefficient of (~)0 and another for the coefficient of ~:

(S00 )2 − p2 (x) = 0 ,
(3.2.9)
2S00 S10 − iS000 = 0 .

The first equation is easily solved:

Z x
S00 = ±p(x) → S0 (x) = ± p(x0 )dx0 (3.2.10)
x0

where x0 is a constant of integration to be adjusted. The next equation allows us to find

S1 which is in fact imaginary:

i S000 i (±p0 (x)) i p0

S10 = = = . (3.2.11)
2 S00 2 (±p(x)) 2p

This is readily solved to give

i S1 (x) = − 12 ln p(x) + C 0 . (3.2.12)

Let us now reconstruct the wavefunction to this order of approximation:

   
i 2 i
ψ(x) = exp (S0 + ~S1 + O(~ )) ' exp S0 exp [iS1 ] (3.2.13)
~ ~

Using our results for S0 and S1 we have that the approximate solution is

i x
 Z 
p(x )dx exp − 12 log p(x) + C 0 .
0 0
 
ψ(x) = exp ± (3.2.14)
~ x0
56 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

We thus have
i x
 Z 
A 0 0
ψ(x) = p exp ± p(x )dx . (3.2.15)
p(x) ~ x0

This is the basic solution in the WKB approximation. We do not attempt to normalize this
wavefunction because, in fact, the region of validity of this approximation is still unclear.
Observables for the basic solution:

i) Probability density:
|A|2 |A|2
ρ = ψ∗ψ = = , (3.2.16)
p(x) mv(x)
where v(x) is the local classical velocity. Note that ρ is higher where v is small as
the particle lingers in those regions and is more likely to be found there. This is an
intuition we developed long ago and is justified by this result.

ii) Probability current: In the language of the polar decomposition (3.1.9) of the wave-
function the basic solution corresponds to
Z x
S(x) = p(x0 )dx0 (3.2.17)
x0

Note that, as anticipated below equation (3.1.15) the gradient of S in the basic solution
is the local momentum. Recalling the result (3.1.14) for the current,

1 ∂S
J = ρ , (3.2.18)
m ∂x
and therefore,
|A|2 p(x) |A|2
J(x) = = . (3.2.19)
p(x) m m
The fact that the current is a constant should not have taken us by surprise. A
position-dependent current for an energy eigenstate is not possible, as it would violate
the current conservation equation ∂x J(x) + ∂t ρ = 0, given that ρ is time independent.

We con now write the general solutions that can be built from the basic solution and
apply to classically allowed and classically forbidden regions.
On the allowed region E − V (x) > 0 we write p2 (x) = ~2 k 2 (x), with k(x) > 0 and hence the
general solution is a superposition of two basic solutions with waves propagating in opposite
directions:
 Z x   Z x 
A 0 0 B 0 0
ψ(x) = p exp i k(x )dx + p exp −i k(x )dx . (3.2.20)
k(x) x0 k(x) x0
3.2. WKB APPROXIMATION SCHEME 57

Note that the first wave, with coefficient A moves to the right while the second wave,
with coefficient B moves to the left. This can be seen by recalling that the above energy
eigenstate ψ(x) is accompanied by the time factor e−iEt/~ when forming a full solution of
the Schrödinger equation. Moreover, the first phase (accompanying A) grows as x grows,
while the second phase becomes more negative as x grows.
On the forbidden region p2 = −~2 κ2 (x) so we can take p(x) = iκ(x) in the solution,
with κ > 0, to find
Z x   Z x 
C 0 0 D 0 0
ψ(x) = p exp κ(x )dx + p exp − κ(x )dx (3.2.21)
κ(x) x0 κ(x) x0

The argument of the first exponential becomes more positive as x grows. Thus the first
term, with coefficient C, is an increasing function as x grows. The argument of the second
exponential becomes more negative x grows. Thus the second term, with coefficient D, is
a decreasing function as x grows.

3.2.1 Validity of the approximation

To understand more concretely the validity of our approximations, we reconsider the ex-
pansion (3.2.8) of the differential equation:
(S00 )2 − p2 + ~ 2S00 S10 − iS000 + O ~2 = 0



(3.2.22)
We must have that the O (~) terms in the differential equation are much smaller, in magni-
tude, than the O (1) terms. At each of these orders we have two terms that are set equal to
each other by the differential equations. It therefore suffices to check that one of the O (~)
terms is much smaller than one of the O (1) terms. Thus, for example, we must have
|~S00 S10 |  |S00 |2 . (3.2.23)
Canceling one factor of |S00 | and recalling that |S00 | = |p| we have
|~S10 |  |p| . (3.2.24)
From (3.2.11) we note that |S10 | ∼ |p0 /p| and therefore we get
p0
~  |p| . (3.2.25)
p
There are two useful ways to think about this relation. First we write it as
~ dp dp
 |p| → λ  |p| (3.2.26)
p dx dx
which tells us that the changes in the local momentum over a distance equal to the de
Broglie wavelength are small compared to the momentum. Alternatively we write (3.2.25)
as follows:
p0 d 1
~ 2  1 → ~  1. (3.2.27)
p dx p
58 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

This now means

dλ
 1. (3.2.28)
dx

The de Broglie wavelength must vary slowly. Note the consistency with units, the left-hand
side of the inequality being unit free. More intuitive, perhaps, is the version obtained by
multiplying the above by λ
dλ
λ  λ. (3.2.29)
dx
This tells us that the variation of the de Broglie wavelength λ over a distance λ must be
much smaller that λ.
It is not hard to figure out what the above constraints tell us about the rate of change
of the potential. Finally connect to the potential. Taking one spatial derivative of the
equation p2 = 2m(E − V (x)) we get

dV dV 1
|pp0 | = m → = |pp0 | . (3.2.30)
dx dx m

Multiplying by the absolute value of λ = h/p

dV 2π~ 0 p2
λ(x) = |p |  , (3.2.31)
dx m m

where the last inequality follows from (3.2.25). Hence, we find that

dV p2
λ(x)  . (3.2.32)
dx 2m

The change in the potential over a distance equal to the de Broglie wavelength must be
much smaller than the kinetic energy. This is the precise meaning of a slowly changing
potential in the WKB approximation.
The slow variation conditions needed for the basic WKB solutions to be accurate fail
near turning points. This could be anticipated since at turning points the local momentum
becomes zero and the de Broglie wavelength becomes infinite. Under general conditions,
sufficiently near a turning point the potential V (x) is approximately linear, as shown in
Figure 3.1. We then have

V (x) − E = g(x − a) , g > 0. (3.2.33)

In the allowed region x < a the local momentum is

p2 = 2m((E − V (x)) = 2mg(a − x) . (3.2.34)

3.3. CONNECTION FORMULA 59

Figure 3.1: The slow-varying conditions in WKB are violated at turning points.

As a result, the de Broglie wavelength is given by

2π~ 2π~
λ(x) = = √ √ . (3.2.35)
p 2mg a − x

Taking a derivative, we find

dλ π~ 1
= √ . (3.2.36)
dx 2mg (a − x)3/2

The right-hand side goes to infinity as x → a and therefore the key condition (3.2.28) is
violated as we approach turning points. Our basic WKB solutions can be valid only as
long as we remain away from turning points. If we have a turning point, such as x = a in
the figure, we need a ‘connection formula’ that tells us how a solution far to the left and a
solution far to the right of the turning point are related when they together form a single
solution. We will consider a connection formula right below.

3.3 Connection formula

Let us first explain and then use a set of connection formulae, leaving their derivation for
next section. The connection formulae refer to solutions away from a turning point x = a
separating a classically allowed region to the left and a classically forbidden region to the
right. This is the situation illustrated in Figure 3.2.
For such turning point at x = a the WKB solutions to the right are exponentials that
grow or decay and the WKB solutions to the left are oscillatory functions. They connect
60 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

Figure 3.2:

consistent with the following relations

Z a   Z x 
2 0 0 π 1 0 0
p cos k(x )dx − ⇐= p exp − κ(x )dx (3.3.1)
k(x) x 4 κ(x) a

Z a  Z x 
1 π 1
−p sin k(x0 )dx0 − =⇒ p exp κ(x0 )dx0 (3.3.2)
k(x) x 4 κ(x) a

In the first relation the arrow tells us that if the solution is a pure decaying exponential to
the right of x = a the solution to the left of x = a is accurately determined and given by
the phase-shifted cosine function the arrow points to. The second relation says that if the
solution to the left of x = a is of an oscillatory type, the growing part of the solution to
the right of x = a is accurately determined and given by the exponential the arrow points
to. The decaying part cannot be reliably determined. As we will elaborate upon later, any
connection formula is not to be used in the direction that goes against the arrow.

Example: Find a quantization condition for the energies of bound states in a monoton-
ically increasing potential V (x) that has a hard wall at x = 0. Assume V (x) increases
without bound, as illustrated in Figure 3.3.
Let E denote the energy of our searched-for eigenstate. Clearly, the energy and the
potential V (x) determine the turning point x = a. The solution for x > a must only have a
decaying exponential since the forbidden region extends forever to the right of x = a. The
wavefunction for x > a is therefore of the type on the right-side of the connection formula
(3.3.1). This means that we have an accurate representation of the wavefunction to the left
of x = a. Adjusting the arbitrary normalization, we have
Z a 
1 0 0 π
ψ(x) = p cos k(x )dx − 4 , 0 ≤ x  a . (3.3.3)
k(x) x
3.3. CONNECTION FORMULA 61

Figure 3.3: A monotonically increasing potential with a hard wall at x = 0. For an energy eigenstate
of energy E the turning point is at x = a.

Since we have a hard wall, the wavefunction must vanish for x = 0. The condition ψ(0) = 0
requires that
Z a
cos ∆ = 0 , with ∆ = k(x0 )dx0 − π4 . (3.3.4)
0

This is satisfied when

Z a
∆= k(x0 )dx0 − π
4 = π
2 + nπ , n ∈ Z. (3.3.5)
0

The quantization condition is therefore

Z a
k(x0 )dx0 = n + 3


4 π , n = 0, 1, 2, . . . . (3.3.6)
0

Negative integers are not allowed because the left-hand side is manifestly positive. The
above is easy to use in practice. Using the expression for k(x) in terms of E and V (x) we
have
Z ar
2m
(E − V (x0 )) dx0 = n + 34 π , n = 0, 1, 2, . . .


2
(3.3.7)
0 ~

In some special cases a can be calculated in terms of E and the integral can be done
analytically. More generally, this is done numerically, exploring the value of the integral
on the left hand side as a function of E and selecting the energies for which it takes the
quantized values on the right-hand side.
62 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

Ra Ra Rx
Let us rewrite the wavefunction using x = 0 − 0 :
Z a Z x 
1 0 0 π 0 0
ψ(x) = p cos k(x )dx − − 4 k(x )dx
k(x) 0 0
 Z x 
1 0 0
= p cos ∆ − k(x )dx (3.3.8)
k(x) 0
Z x 
sin ∆ 0 0
= p sin k(x )dx ,
k(x) 0

where we expanded the cosine of a sum of angles and recalled that cos ∆ = 0. In this form
it is manifest that the wavefunction vanishes at x = 0. More interestingly, the quantization
condition (3.3.6) indicates that the excursion of the phase in the solution from 0 to a is a
bit higher than nπ (but less than (n + 1)π). Thus the WKB wavefuntion produces the n
nodes the n-th excited state must have, even though this wavefunction is not reliable all to
way to x = a.

3.4 Airy functions and connection formulae

(3.4.9)

V (x) − E ' g(x − a) with g > 0 for x ∼ a (3.4.10)

Solutions
 Z x  Z x 
A 0 0 B 0 0
ψ(x) = p exp − κ(x )dx
+p exp κ(x )dx xa (3.4.11)
κ(x) a κ(x) a
 Z a   Z a 
C 0 0 D 0 0
ψ(x) = p exp i k(x )dx + p exp −i k(x )dx x  a (3.4.12)
k(x) x k(x) x
3.4. AIRY FUNCTIONS AND CONNECTION FORMULAE 63

where
2m 2mg
k2 ≡ (E − V (x)) ' 2 (a − x) x≤a (3.4.13)
~2 ~
2m 2mg
κ2 ≡ 2
(V (x) − E) ' 2 (x − a) x≥a (3.4.14)
~ ~
Idea: Solve Schrodinger equation
~2 00
− ψ + (V (x) − E)ψ = 0 (3.4.15)
2m
with the exact linear potential, i.e.
~2 00
− ψ + g(x − a)ψ = 0 (3.4.16)
2m
• Solve (3.4.16) exactly.
• Match it to the x  a version of (3.4.11) or x  a version of (3.4.12).
• Find the required relations between coefficients!
Solve (3.4.16). Remove units, find length scale.
 13
~2 ~2

= gL =⇒ L = (3.4.17)
mL2 mg
so define  1
2mg 3
u= (x − a) ≡ η(x − a) (3.4.18)
~2
thus (3.4.16) becomes
d2 ψ
− uψ = 0 (3.4.19)
du2
with solution
ψ = αAi (u) + βBi (u) (3.4.20)
where α and β are constants and Ai (u), Bi (u) are Airy functions:
1
 12 √1π |u|− 4 e−ξ

u  1,
Ai (u) ' (3.4.21)
 √1 |u|− 41 cos ξ − π
u  −1.
π 4

1
 √1π |u|− 4 eξ

u  1,
Bi (u) ' (3.4.22)
− √1 |u|− 14 sin ξ − π
u  −1.
π 4

with
3
ξ ≡ 32 |u| 2 . (3.4.23)
These are in fact WKB solutions and special cases of connection conditions! (Explain)
64 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

3.4.1 How bad are the errors?

Take a WKB solution and find the DE it satisfies

1 2 3
ψ(u) = 1 e− 3 |u| 2 (3.4.24)
u 4

solves
d2 ψ  5 1
− u + ψ=0 (3.4.25)
du2 16 u2
so clearly for u  1 the extra term is negligible.
To evaluate (3.4.11) and (3.4.12), determine κ(x) and k(x). Using (3.4.13) and (3.4.14):

k 2 = η 3 (a − x) = −η 2 u = η 2 |u| u<0 (3.4.26)

κ2 = η 3 (x − a) = +η 2 u u>0 (3.4.27)

Using 0 = d
the WKB condition is |k 0 |  |k 2 | From ...
dx ,

η3 η3 η2
|2kk 0 | = η 3 =⇒ |k 0 | = = = (3.4.28)
2|k| 2η|u| 2|u|

k 2 = η 2 |u| thus

η2 3 1
|k 0 |  k 2 ,  η 2 |u| =⇒ |u| 2  =⇒ |u|  0.63 (3.4.29)
2|u| 2

Two integrals to estimate

Z x Z xp
0 0 2 3 3 x
x>a: κ(x )dx = η 3 (x0 − a)dx0 = η 2 (x0 − a) 2
a a 3 a
2 3 3 2 3 2 3
= η 2 (x − a) 2 = u 2 = |u| 2 = ξ (3.4.30)
3 3 3
Z a Z ap  a
0 0 3 2 0 32
x<a: k(x )dx = η 3 (a − x0 )dx0 = η − (a − x )
2
x x 3 x
2 3 3 2 3
= η 2 (a − x) 2 = |u| 2 = ξ (3.4.31)
3 3

both integrals are equal to ξ.

1 1 1 1
p = 1 1 , p = 1 1 (3.4.32)
κ(x) η 2 |u| 4 k(x) η 2 |u| 4
3.4. AIRY FUNCTIONS AND CONNECTION FORMULAE 65

1
(3.4.11) and (3.4.12), let {A, B, C, D} → η 2 {A, B, C, D} √1π to cancel the extra factor and
produce the ... constants
1 1
|u|− 4 |u|− 4
ψ(x) = A √ e−ξ + B √ eξ u1
π π
= 2AAi (u) + BBi (u) (3.4.33)

1 1
|u|− 4 |u|− 4
ψ(x) = C √ eiξ + D √ e−iξ u  −1 (3.4.34)
π π
Note that
1
|u|− 4 π
Ai + iBi = √ e−i(ξ− 4 ) (3.4.35)
π
1
|u|− 4 π
Ai − iBi = √ ei(ξ− 4 ) (3.4.36)
π
thus
1
i π4 |u|− 4
e (Ai − iBi ) = √ eiξ (3.4.37)
π
1
−i π4 |u|− 4
e (Ai + iBi ) = √ e−iξ (3.4.38)
π
Now back in (3.4.34):
π π
ψ(x) = Cei 4 (Ai − iBi ) + De−i 4 (Ai + iBi )
 π π
  π π

= Cei 4 + De−i 4 Ai + iDe−i 4 − iCei 4 Bi (3.4.39)

Finally equate (one solution):

π π
2A = Cei 4 + De−i 4 (3.4.40)
i π4 −i π4
iB = Ce − De =⇒ (3.4.41)

1 π
C = e−i 4 (2A + iB) (3.4.42)
2
1 iπ
D = e 4 (2A − iB) (3.4.43)
2
back in (3.4.12)
 Z a   Z a 
1 (2A + iB) 0 0 π 1 (2A − iB) 0 0 π
ψ(x) = p exp i k(x )dx − + p exp −i k(x )dx − =⇒
2 k(x) x 4 2 k(x) x 4
66 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

Z a  Z a 
2A 0 0 π B 0 0 π
ψ(x) = p cos k(x )dx − −p sin k(x )dx − (3.4.44)
k(x) x 4 k(x) x 4

Now discuss a subtlety. The formulas are in reality only usable in one direction with partial
results. Some terminology helps. We always speak having in mind a fixed turning point. If
we say we have a growing exponential at a turning point we mean we have a solution that
grows as we move away from the turning point towards the classically forbidden region.
Similarly, a decaying exponential means our solution decays as we move away from the
turning point towards the classically forbidden region. In summary the connection arrow
can go from a decaying exponential into an oscillatory solution and can go from an oscilla-
tory solution into a growing exponential.

3.4.2 The other connection conditions

This time the turning point is at x = b, with the classically allowed region to the right of it
and the classically forbidden region to the left of it.

 Z b  Z x 
1 0 0 2 π
p exp − κ(x )dx =⇒ p cos k(x0 )dx0 − (3.4.45)
κ(x) x k(x) b 4
Z b  Z x 
1 1 π
− p exp κ(x0 )dx0 ⇐= p sin k(x0 )dx0 − (3.4.46)
κ(x) x k(x) b 4
For the first relation, if there is only a decaying exponential to the left, the wavefunction
is definitely without the growing exponential, and the wavefunction to the right of x = b is
accurately determined. This does not work in the reverse direction because a small error in
the oscillatory function would give a growing exponential to the left of for x = b that would
overtake the predicted decaying solution.
For the second relation, the stated direction (from right to left) is reliable: an small
error on the right side of x = b would produce a decaying exponential, thus a small error
on the left-side of x = b. The reverse direction does not work: a small error to the left of
x = b, a decaying exponential, would produce a large error in the right-hand side.
3.5. TUNNELLING THROUGH A BARRIER 67

In summary, in all cases of the connection conditions, relative to a turning point,

We can connect away from a decaying exponential and into a growing exponential.
(3.4.47)

3.5 Tunnelling through a barrier

Figure 3.4: Tunneling in the WKB approximation. The energy E must be smaller than the height
of the potential, and the barrier must be wide and smooth.

We want to find the tunneling probability T for a wave of energy incident on a smoothly
varying wide barrier. The energy E of the wave must be smaller than the height of the
potential. In this problem there is an incident wave, a reflected wave and a transmitted
wave, and the associated WKB expressions will have amplitudes controlled by constants
A, B, and F , respectively. The situation is illustrated in Figure 3.4.
Remarks:
1) Expect T to be small. Little probability flux goes through and |A| ≈ |B|.

2) For x  b there is just an outgoing wave with amplitude controlled by F .

3) Within the barrier the component that decays as x grows is more relevant that the
component that grows. It is the only component that can be estimated reliably.
Consider the transmitted right-moving wave valid for x  b
 Z x 
F
ψtr (x) = p exp i k(x0 )dx0 − i π4 , x  b. (3.5.1)
k(x) b

This is a WKB solution with an extra phase of π/4 chosen to make the argument of the
exponential have the familiar form appearing in the connection formulae. Expanding the
68 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

exponential
Z x  Z x 
F 0 0 π iF 0 0 π
ψtr (x) = p cos k(x )dx − 4 +p sin k(x )dx − 4 , x  b . (3.5.2)
k(x) b k(x) b

This is in standard form. We can now match the second term to an exponential that grows
as we move to the left of x = b, by using (3.4.46)
Z b 
iF 0 0
ψ(x)barr = −p exp κ(x )dx , axb. (3.5.3)
κ(x) x

The subscript ‘barr’ indicates a solution in the barrier region. If we attempted to match
the first term in (3.5.2) we would get an exponential that decays as we move to the left of
x = b and it is unreliable given the growing exponential. We can now refer this solution to
the point x = a
Z b Z x 
iF 0 0 0 0
ψ(x)barr = − p exp κ(x )dx − κ(x )dx a  x  b. (3.5.4)
κ(x) a a

Defining
Z b
θ≡ κ(x0 )dx0 (3.5.5)
a
we have  Z x
iF eθ

0 0
ψ(x)barr = −p exp − κ(x )dx a  x  b. (3.5.6)
κ(x) a

Since this is a decaying exponential to the right of x > a we can connect it to a solution to
the left of x < a using (3.3.1)
Z a
2iF eθ

0 0 π
ψ(x) = − p cos k(x )dx − 4 . (3.5.7)
k(x) x

This is a superposition of two waves, a wave ψinc incident on the barrier and a wave ψref
reflected from the barrier. The incident part is
 Z a
iF eθ

0 0 π
ψinc (x) = − p exp −i k(x )dx + i 4 . (3.5.8)
k(x) x

The sign in front of the integral may seem unusual for a wave moving to the right, but
it is correct because the argument x appears in the lower limit of the integration. The
transmission coefficient T is the ratio of the transmitted probability current over the incident
probability current. Given the result in (3.2.19) we have

probability current for ψtr |F |2

T = = = e−2θ . (3.5.9)
probability current for ψinc | − iF eθ |2
3.5. TUNNELLING THROUGH A BARRIER 69

This is the well-known exponential suppression of the transmission coefficient. Using the
earlier definition of θ the result is
 Z b 
Twkb = exp −2 κ(x0 )dx0 . (3.5.10)
a

We added the subscript ‘wkb’ to emphasize that this is the WKB approximation to the
exact transmission coefficient. The integral extends in between the two turning points and
captures information about the height and the width of the barrier. The integrand, as well
as the turning points, depend on the energy as we can display by using the explicit value
of κ(x) :
 Z b r 2m 
Twkb = exp −2 (V (x 0 ) − E) dx0 . (3.5.11)
a ~2
The WKB approximation only captures the exponentially decaying part of the transmission
coefficient. There are corrections that are written as a prefactor to the exponential. These
are not determined in this approximation.

Example. Use the WKB approximation to estimate the transmission probability T for the
rectangular barrier (
V0 for |x| < a ,
V (x) = (3.5.12)
0 , otherwise.
Assume the barrier is large. In terms of the familiar unit-free constant z0 used to characterize
square wells, this means that
2mV0 a2
z02 ≡  1. (3.5.13)
~2
Large barrier means large z0 or large V0 a2 . Moreover we assume E smaller than V0 ; we
cannot expect the approximation to work as the energy approaches the top of the barrier.
Compare the WKB result for T with the exact result.
Solution. The WKB estimation, using (3.5.11) is immediate. Since the barrier extends
from x = −a to x = a and the potential is constant we have
 Z a r 2m 
0
Twkb = exp −2 (V0 − E) dx . (3.5.14)
−a ~2

The integral can be done and we find

 4a p 
Twkb = exp − 2m(V0 − E) . (3.5.15)
~
This is the answer in the WKB approximation. In terms of z0 this reads
r
 E 
Twkb ' exp −4z0 1 − . (3.5.16)
V0
70 CHAPTER 3. WKB AND SEMICLASSICAL APPROXIMATION

The validity of the WKB approximation requires the argument in the exponent to be large.
This is why we need z0  1 and the energy not to approach V0 . When E is very small
compared to V0 , we have
T ∼ exp(−4z0 ) . (3.5.17)
√
Since z0 ∼ a V0 , this result is the basis for the claim that the exponential suppression of
the tunneling probability is proportional to the width of the well and the square root of its
height.
The exact formula for the tunneling probability of a square barrier has been calculated
before, and it is given by

1 V02  2a p 
= 1+ sinh2 2m(V0 − E) . (3.5.18)
T 4E(V0 − E) ~

This formula will allow us to confirm the WKB exponential suppression and to find the
prefactor. Under the conditions z0  1 and V0 − E finite, the argument of the sinh function
is large so this function can be replaced by its growing exponential (sinh x ∼ 12 ex ):

1 V0  4a p 
' 1+ E
exp 2m(V0 − E) , (3.5.19)
T 16E(1 − V0 )
~

where we also replaced V0 − E → V0 in the prefactor. The additive unit on the right-hand
side can be neglected and we have
 4a p 
T ' 16 VE0 (1 − E
V0 ) exp − 2m(V0 − E) . (3.5.20)
~
This result gives the same in exponential suppression as the WKB result (3.5.15). It also
gives us a good approximation to the prefactor.

The WKB approximation is often used for the estimation of lifetimes. The physical
situation is represented in Figure 3.5. We have a particle of mass m and energy E localized
between the turning points x = a and x = b of the potential. The classical particle cannot
escape because of the energy barrier stretching from x = b to x = c. The quantum particle,
however, can tunnel. The state of the quantum particle when localized between a and b
is not strictly an energy eigenstate because the wavefunction for any energy eigenstate is
nonzero for x > c. Our goal is to determine the lifetime τ of the particle. This is done by
using some classical estimates as well as the quantum transmission probability.
We first show that the lifetime τ is the inverse of B, the tunneling probability per unit
time. To see this we examine the function P (t) that represents the probability to have the
particle localized within [a, b] at time t, if it was there at t = 0. The lifetime is said to be τ
if P (t) has the time dependence P (t) = e−t/τ . To see that we have such a situation when
the tunneling rate B is constant note that


P (t + dt) = P (t) · probability that it does not tunnel in the next dt . (3.5.21)
3.5. TUNNELLING THROUGH A BARRIER 71

Figure 3.5: Estimating the lifetime of a particle with energy E temporarily localized in x ∈ [a, b].

Therefore


P (t + dt) = P (t) · 1 − Bdt → P (t + dt) − P (t) = −BP (t) dt . (3.5.22)
We thus have the differential equation, and solution,
dP
= −B P (t) → P (t) = e−Bt , (3.5.23)
dt
from which we identify, as claimed, that
1
τ = . (3.5.24)
B
The tunneling rate B or tunneling probability per unit time is estimated by counting the
number of times nhit the classical particle, bouncing between x = a and x = b, hits the
barrier at x = b per unit time, and multiplying this number by the tunneling probability T :
T
B = nhit T = , (3.5.25)
∆t
where ∆t is the time the classical particle takes to go from b to a and back to b:
Z b Z b
dx dx
∆t = 2 = 2m . (3.5.26)
a v(x) a p(x)

We now can put all the pieces together, using the WKB approximation for T . We find
Z b  Z c
∆t dx 
τ = ' 2m · exp 2 κ(x)dx . (3.5.27)
T a p(x) b

The smaller the tunneling probability, the larger the lifetime of the localized state. Note
that the factor ∆t carries the units of the result. The above result can easily fail to be
accurate, as the WKB approximation for T does not give the prefactor multiplying the
exponential suppression.
MIT OpenCourseWare
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8.06 Quantum Physics III

Spring 2018

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Chapter 4

Time Dependent Perturbation

Theory

c B. Zwiebach

4.1 Time dependent perturbations

We will assume that, as before, we have a Hamiltonian H (0) that is known and is time
independent. Known means we know the spectrum of energy eigenstates and the energy
eigenvalues. This time the perturbation to the Hamiltonian, denoted as δH(t) will be time
dependent and, as a result, the full Hamiltonian H(t) is also time dependent

H(t) = H (0) + δH(t) . (4.1.1)

While H (0) has a well-defined spectrum, H(t) does not. Being time dependent, H(t) does
not have energy eigenstates. It is important to remember that the existence of energy
eigenstates was predicated on the factorization of solutions Ψ(x, t) of the full Schrödinger
equation into a space-dependent part ψ(x) and a time dependent part that turned out to be
e−iEt/~ , with E the energy. Such factorization is not possible when the Hamiltonian is time
dependent. Since H(t) does not have energy eigenstates the goal is to find the solutions
|Ψ(x, t)i directly. Since we are going to focus on the time dependence, we will suppress the
labels associated with space. We simply say we are trying to find the solution |Ψ(t)i to the
Schrödinger equation
∂
i~ |Ψ(t)i = H (0) + δH(t) |Ψ(t)i .


(4.1.2)
∂t
In typical situations the perturbation δH(t) vanishes for t < t0 , it exists for some finite
time, and then vanishes for t > tf (see Figure 4.1). The system starts in an eigenstate of
H (0) at t < t0 or a linear combination thereof. We usually ask: What is the state of the
system for t > tf ? Note that both initial and final states are nicely described in terms of
eigenstates of H (0) since this is the Hamiltonian for t < t0 and t > tf . Even during the

73
74 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

Figure 4.1: Time dependent perturbations typically exist for some time interval, here from t0 to tf .

time when the perturbation is on we can use the eigenstates of H (0) to describe the system,
since these eigenstates form a complete basis, but the time dependence is very nontrivial.
Many physical questions can be couched in this language. For example, assume we have
a hydrogen atom in its ground state. We turn on EM fields for some time interval. We can
then ask: What are the probabilities to find the atom in each of the various excited states
after the perturbation turned off?

4.1.1 The interaction picture

In order to solve efficiently for the state |Ψ(t)i we will introduce the Interaction Picture of
Quantum Mechanics. This picture uses some elements of the Heisenberg picture and some
elements of the Schrödinger picture. We will use the known Hamiltonian H (0) to define
some Heisenberg operators and the perturbation δH will be used to write a Schrödinger
equation.
We begin by recalling some facts from the Heisenberg picture. For any Hamiltonian,
time dependent or not, one can determine the unitary operator U(t) that generates time
evolution:
|Ψ(t)i = U(t)|Ψ(0)i . (4.1.3)
The Heisenberg operator ÂH associated with a Schrödinger operator Âs is obtained by
considering a rewriting of expectation values:

hΨ(t)|Âs |Ψ(t)i = hΨ(0)|U † (t)Âs U(t)|Ψ(0)i = hΨ(0)|ÂH |Ψ(0)i , (4.1.4)

where
AH ≡ U † (t)Âs U(t) . (4.1.5)
This definition applies even for time dependent Schrödinger operators. Note that the oper-
ator U † brings states to rest:

U † (t)|Ψ(t)i = U † (t)U(t)|Ψ(0)i = |Ψ(0)i . (4.1.6)

In our problem the known Hamiltonian H (0) is time independent and the associated unitary
time evolution operator U0 (t) takes the simple form
 iH (0) t 
U0 (t) = exp − . (4.1.7)
~
4.1. TIME DEPENDENT PERTURBATIONS 75

The state |Ψ(t)i in our problem evolves through the effects of H (0) plus δH. Motivated
by (4.1.6) we define the auxiliary ket Ψ(t)
e as the ket |Ψ(t)i partially brought to rest
through H :(0)

 iH (0) t 
Ψ(t)
e ≡ exp Ψ(t) . (4.1.8)
~

Expect that Schrödinger equation for Ψ(t)

e will be simpler, as the above must have taken
care of the time dependence generated by H (0) . Of cours, if we can determine Ψ(t)
e we
can easily get back the desired state Ψ(t) inverting the above relation to find

 iH (0) t 
Ψ(t) = exp − Ψ(t)
e . (4.1.9)
~

Our objective now is to find the Schrödinger equation for Ψ(t)

e . Taking the time
derivative of (4.1.8) and using (4.1.2)

d e  iH (0) t 
i~ Ψ(t) = −H (0) Ψ(t)
e + exp (H (0) + δH(t)) Ψ(t)
dt " ~ #
 iH (0) t   iH (0) t 
(0) (0)
= −H + exp (H + δH(t)) exp − Ψ(t)
e
~ ~
 iH (0) t   iH (0) t 
= exp δH(t) exp − Ψ(t)
e , (4.1.10)
~ ~

where the dependence on H (0) cancelled out. We have thus found the Schrödinger equation

d e
i~ Ψ(t) = δH(t)
f Ψ(t)
e . (4.1.11)
dt

where the operator δH(t)

f is defined as

 iH (0) t   iH (0) t 
δH(t)
f ≡ exp δH(t) exp − . (4.1.12)
~ ~

Note that as expected the time evolution left in Ψ(t)

e is generated by δH(t)
f via a Schrödinger
equation. The operator δH(t)
f is nothing else but the Heisenberg version of δH generated
(0)
using H ! This is an interaction picture, a mixture of Heisenberg’s and Schrödinger pic-
ture. While we have some Heisenberg(0) operators there is still a time dependent state
Ψ(t)
e and a Schrödinger equation for it.
76 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

How does it all look in an orthonormal basis? Let |ni be the complete orthonormal basis
of states for H (0) :
H (0) |ni = En |ni . (4.1.13)
This time there is no need for a (0) superscript, since neither the states nor their energies
will be corrected (there are no energy eigenstates in the time-dependent theory). We then
write an ansatz for our unknown ket:
X
Ψ(t)
e = cn (t)|ni . (4.1.14)
n

Here the functions cn (t) are unknown. This expansion is justified since the states |ni form
a basis, and thus at all times they can be used to describe the state of the system. The
original wavefunction is then:
 iH (0) t  X 
iEn t

Ψ(t) = exp − Ψ(t)
e = cn (t) exp − |ni . (4.1.15)
~ n
~

Note that the time dependence due to H (0) is present here. If we had δH = 0 the state
Ψ(t)
e would be a constant, as demanded by the Schrödinger equation (4.1.11) and the
cn (t) would be constants. The solution above would give the expected time evolution of the
states under H (0) .
To see what the Schrödinger equation tells us about the functions cn (t) we plug the
ansatz (4.1.14) into (4.1.11):
d X X
i~ cm (t)|mi = δH(t)
f cn (t)|ni (4.1.16)
dt m n

Using dots for time derivatives and introducing a resolution of the identity on the right-hand
side we find
X X X
i~ċm (t)|mi = |mihm|δH(t)
f cn (t)|ni
m m n
X X
= |mi hm|δH(t)|nic
f n (t)
m n
X
= δH
f mn (t)cn (t)|mi . (4.1.17)
m,n

Here we have used the familiar matrix element notation

f mn (t) ≡ hm|δH(t)|ni
δH f . (4.1.18)

Equating the coefficients of the basis kets |mi in (4.1.17) we get the equations
X
i~ ċm (t) = δH
f mn (t) cn (t) . (4.1.19)
n
4.1. TIME DEPENDENT PERTURBATIONS 77

The Schrödinger equation has become an infinite set of coupled first-order differential equa-
tions. The matrix elements in the equation can be simplified a bit by passing to un-tilde
variables:
 (0)  (0) 
f mn (t) = m exp iH t δH(t) exp − iH t n

δH
~ ~
  (4.1.20)
i
= exp (Em − En )t hm|δH(t)|ni .
~

If we define
Em − En
ωmn ≡ , (4.1.21)
~
we then have
f mn (t) = eiωmn t δHmn (t) .
δH (4.1.22)
The coupled equations (4.1.19) for the functions cn (t) then become

X
i~ ċm (t) = eiωmn t δHmn (t)cn (t) . (4.1.23)
n

4.1.2 Example (based on Griffiths Problem 9.3)

Consider a two-state system with basis states |ai and |bi, eigenstates of H (0) with energies
Ea and Eb , respectively. Call
ωab ≡ (Ea − Eb )/~ . (4.1.24)
Now take the perturbation to be a matrix times a delta function at time equal zero. Thus
the perturbation only exists for time equal zero:
 
0 α
δH(t) = δ(t) ≡ U δ(t) , (4.1.25)
α∗ 0

where α is a complex number. With the basis vectors ordered as |1i = |ai and |2i = |bi we
have  
Uaa Uab ∗
U = , with Uaa = Ubb = 0 and Uab = Uba = α. (4.1.26)
Uba Ubb
There is a sudden violent perturbation at t = 0 with off-diagonal elements that should
produce transition. Take the system to be in |ai for t = −∞, what is the probability that
it is in |bi for t = +∞?
Solution: First note that if the system is in |ai at t = −∞ it will remain in state |ai until
t = 0− , that is, just before the perturbation turns on. This is because |ai is an energy
eigenstate of H (0) . In fact we have, up to a constant phase,

|Ψ(t)i = e−iEa t/~ |ai , for − ∞ < t ≤ 0− . (4.1.27)

78 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

We are asked what will be the probability to find the state in |bi at t = ∞, but in fact, the
answer is the same as the probability to find the state in |bi at t = 0+ . This is because the
perturbation does not exist anymore and if the state at t = 0+ is

|Ψ(0+ )i = γa |ai + γb |bi , (4.1.28)

with γ1 and γ2 constants, then the state for any time t > 0 will be

|Ψ(t)i = γa |aie−iEa t/~ + γb |bie−iEb t/~ . (4.1.29)

The probability pb (t) to find the state |bi at time t will be

pb (t) = |hb|Ψ(t)i|2 = γb e−iEb t/~ = |γb |2 , (4.1.30)

and, as expected, this is time independent. It follows that to solve this problem we must
just find the state at t = 0+ and determine the constants γ1 and γ2 .
Since we have two basis states the unknown tilde state is

Ψ(t)
e = ca (t)|ai + cb (t)|bi , (4.1.31)

and the initial conditions are stating that the system begins in the state |ai are

ca (0− ) = 1 , cb (0− ) = 0 . (4.1.32)

The differential equations (4.1.23) take the form

i~ ċa (t) = eiωab t δHab (t)cb (t) ,

(4.1.33)
i~ ċb (t) = eiωba t δHba (t)ca (t) .

The couplings are off-diagonal because δHaa = δHbb = 0. Using the form of the δH matrix
elements,

i~ ċa (t) = eiωab t α δ(t) cb (t) ,

(4.1.34)
i~ ċb (t) = e−iωab t α∗ δ(t) ca (t) .

We know that for functions f continuous at t = 0 we have f (t)δ(t) = f (0)δ(t). We now

ask if we are allowed to use such identity for the right-hand side of the above equations. In
fact we can use the identity for e±iωab t but not for the functions ca (t) and cb (t) that, are
expected to be discontinuous at t = 0. They must be so, because they can only change at
t = 0, when the delta function exists. Evaluating the exponentials at t = 0 we then get the
simpler equations

i~ ċa (t) = α δ(t) cb (t) ,

(4.1.35)
i~ ċb (t) = α∗ δ(t) ca (t) .
4.1. TIME DEPENDENT PERTURBATIONS 79

With such singular right-hand sides, the solution of these equations needs regulation. We
will regulate the delta function and solve the problem. A consistency check is that the
solution has a well-defined limit as the regulator is removed. We will replace the δ(t) by
the function ∆t0 (t), with t0 > 0, defined as follows:
(
1/t0 , for t ∈ [0, t0 ] ,
δ(t) → ∆t0 (t) = (4.1.36)
0, otherwise .
R
Note that as appropriate, dt∆t0 (t) = 1, and that ∆t0 (t) in the limit as t0 → 0 approaches
a delta function. If we replace the delta functions in (4.1.37) by the regulator we find, for
t ∈ [0, t0 ]
α
For t ∈ [0, t0 ] : i~ ċa (t) = cb (t) ,
t0
(4.1.37)
α∗
i~ ċb (t) = ca (t) .
t0
For any other times the right-hand side vanishes. By taking a time derivative of the first
equation and using the second one we find that
1 α 1 α∗ |α| 2
 
c̈a (t) = ca (t) = − ca (t) . (4.1.38)
i~ t0 i~ t0 ~t0
This is a simple second order differential equation and its general solution is
   
|α|t |α|t
ca (t) = β0 cos + β1 sin . (4.1.39)
~t0 ~t0
This is accompanied with cb (t) which is readily obtained from the first line in (4.1.37):
i~t0 i|α|   |α|t   |α|t 
cb (t) = ċa (t) = −β0 sin + β1 cos . (4.1.40)
α α ~t0 ~t0
The initial conditions (4.1.32) tell us that in this regulated problem ca (0) = 1 and cb (0) = 0.
Given the solutions above, the first condition fixes β0 = 1 and the second fixes β1 = 0. Thus,
our solutions are:
 
|α|t
For t ∈ [0, t0 ] : ca (t) = cos , (4.1.41)
~t0
 
|α| |α|t
cb (t) = −i sin . (4.1.42)
α ~t0
When the (regulated) perturbation is turned off (t = t0 ), ca and cb stop varying and the
constant value they take is their values at t = t0 . Hence
 
|α|
ca (t > t0 ) = ca (t0 ) = cos , (4.1.43)
~
 
|α| |α|
cb (t > t0 ) = cb (t0 ) = −i sin . (4.1.44)
α ~
80 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

Note that these values are t0 independent. Being regulator independent, we can safely take
the limit t0 → 0 to get
 
|α|
ca (t > 0) = cos , (4.1.45)
~
 
|α| |α|
cb (t > 0) = −i sin . (4.1.46)
α ~
Our calculation above shows that at t = 0+ the state will be
   
+ + |α| |α| |α|
|Ψ(0 )i = |Ψ(0 )i = cos
e a − i sin b . (4.1.47)
~ α ~
With only free evolution ensuing for t > 0 we have (as anticipated in (4.1.29))
   
|α| −iEa t/~ |α| |α|
|Ψ(t)i = cos a e − i sin b e−iEb t/~ . (4.1.48)
~ α ~
The probabilities to be found in |ai or in |bi are time-independent, we are in a superposition
of energy eigenstates! We can now easily calculate the probability pb (t) to find the system
in |bi for t > 0 as well as the probability pa (t) to find the system in |ai for t > 0:
 
|α|
pb (t) = |hb|Ψ(t)i|2 = sin2 ,
~
  (4.1.49)
2 2 |α|
pa (t) = |ha|Ψ(t)i| = cos .
~
Note that pa (t)+pb (t) = 1, as required. The above is the exact solution of this system. If we
had worked in perturbation theory, we would be taking the strength |α| of the interaction
to be small. The answers we would obtain would form the power series expansion of the
above formulas in the limit as |α|/~ is small.

4.2 Perturbative solution

In order to set up the perturbative expansion properly we include a unit-free small parameter
λ multiplying the perturbation δH in the time-dependent Hamiltonian (4.1.1):
H(t) = H (0) + λδH(t) . (4.2.1)
With such a replacement the interaction picture Schrödinger equation for |Ψ(t)i
e in (4.1.11)
now becomes
d e
i~ Ψ(t) = λδH(t)
f Ψ(t)
e . (4.2.2)
dt
As we did in time-independent perturbation theory we start by expanding Ψ(t)e in powers
of the parameter λ:
e (0) (t) + λ Ψ
e (1) (t) + λ2 Ψe (2) (t) + O λ3 .


Ψ(t)
e = Ψ (4.2.3)
4.2. PERTURBATIVE SOLUTION 81

We now insert this into both sides of the Schrödinger equation (4.2.2), and using ∂t for time
derivatives, we find

e (0) (t) + λ i~∂t Ψ

e (1) (t) + λ2 i~∂t Ψ
e (2) (t) + λ3 i~∂t Ψ
e (2) (t) + O λ4


i~∂t Ψ
(4.2.4)
e (0) (t) + λ2 δH e (1) (t) + λ3 δH e (2) (t) + O λ4 .


f Ψ
= λ δH f Ψ f Ψ

The coefficient of each power of λ must vanish, giving us

e (0) (t)
i~∂t Ψ = 0,
e (1) (t)
i~∂t Ψ = δH
f Ψe (0) (t) ,
e (2) (t)
i~∂t Ψ = δH
f Ψe (1) (t) , (4.2.5)
.. ..
. = .
e (n+1) (t)
i~∂t Ψ f Ψ
= δH e (n) (t) .

The origin of the pattern is clear. Since the Schrödinger equation has an explicit λ multi-
plying the right-hand side, the time derivative of the n-th component is coupled to the δH
f
perturbation acting on the (n − 1)-th component.
Let us consider the initial condition in detail. We will assume that the perturbation
turns on at t = 0, so that the initial condition is given in terms of |Ψ(0)i. Since our
Schrödinger equation is in terms of |Ψ(t)i
e we use the relation ((4.1.8)) between them to
conclude that both tilde and un-tilde wavefunctions are equal at t = 0:

|Ψ(0)i
e = |Ψ(0)i . (4.2.6)

Given this, the expansion (4.2.3) evaluated at t = 0 implies that:

e (0) (0) e (1) (0) + λ2 Ψ

e (2) (0) + O λ3 .


Ψ(0)
e = |Ψ(0)i = Ψ +λ Ψ (4.2.7)

This must be viewed, again, as an equation that holds for all values of λ. As a result, the
coefficient of each power of λ must vanish and we have

e (0) (0)
Ψ = Ψ(0) ,
(4.2.8)
e (n) (0)
Ψ = 0, n = 1, 2, 3 . . . .

These are the relevant initial conditions.

Consider now the first equation in (4.2.5). It states that Ψe (0) (t) is time independent.
This is reasonable: if the perturbation vanishes, this is the only equation we get and we
should expect Ψ(t)
e constant. Using the time-independence of Ψ e (0) (t) and the initial
condition we have
e (0) (t) = Ψ
Ψ e (0) (0) = Ψ(0) , (4.2.9)
82 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

and we have solved the first equation completely:

e (0) = Ψ(0) .
Ψ (4.2.10)

Using this result, the O(λ) equation reads:

e (1) (t) = δH
i~∂t Ψ f Ψe (0) (t) = δH(t)
f Ψ(0) . (4.2.11)

The solution can be written as an integral:

Z t f 0)
δH(t
e (1) (t) =
Ψ Ψ(0) dt0 . (4.2.12)
0 i~

Note that by setting the lower limit of integration at t = 0 we have implemented correctly
e (1) (0)i = 0. The next equation, of order λ2 reads:
the initial condition |Ψ

e (2) (t) = δH
i~∂t Ψ f Ψe (1) (t) , (4.2.13)

and its solution is Z t f 0)

δH(t
e (2) (t) =
Ψ e (1) (t0 ) dt0 ,
Ψ (4.2.14)
0 i~
e (1) (t0 ) we now
consistent with the initial condition. Using our previous result to write Ψ
have an iterated integral expression:

Z t f 0 ) Z t0 δH(t
δH(t f 00 )
e (2) (t) =
Ψ dt0 Ψ(0) dt00 . (4.2.15)
0 i~ 0 i~

It should be clear from this discussion how to write the iterated integral expression for
e (k) (t) , with k > 2. The solution, setting λ = 1 and summarizing is then
Ψ
!
 iH (0) t 
Ψ(t) = exp − |Ψ(0)i + |Ψe (1) (t)i + |Ψ
e (2) (t)i + · · · (4.2.16)
~

Let us use our perturbation theory to calculate the probability Pm←n (t) to transition
from |ni at t = 0 to |mi, with m 6= n, at time t, under the effect of the perturbation. By
definition
2
Pm←n (t) = hm|Ψ(t)i . (4.2.17)
Using the tilde wavefunction, for which we know how to write the perturbation, we have
(0) t/~ 2 2
Pm←n (t) = hm|e−iH Ψ(t)
e = hm|Ψ(t)i
e , (4.2.18)
4.2. PERTURBATIVE SOLUTION 83

since the phase that arises from the action on the bra vanishes upon the calculation of the
norm squared. Now using the perturbation expression for |Ψ(t)i
e (setting λ = 1) we have
  2
Pm←n (t) = hm| Ψ(0) + Ψ
e (1) (t) + Ψ
e (2) (t) + . . . . (4.2.19)

Since we are told that |Ψ(0)i = |ni and |ni is orthogonal to |mi we find
2
e (1) (t) + hm Ψ
Pm←n (t) = hm Ψ e (2) (t) + . . . . (4.2.20)

To first order in perturbation theory we only keep the first term in the sum and using our
e (1) (t)i we find
result for |Ψ
2 2
Z t f 0)
δH(t
Z t f 0 )|ni
hm|δH(t
(1)
Pm←n (t) = hm| |ni dt0 = dt0 . (4.2.21)
0 i~ 0 i~

Recalling the relation between the matrix elements of δH f and those of δH we finally have
our result for the transition probability to first order in perturbation theory:

2
t
δH mn (t0 ) 0
Z
(1) 0
Pm←n (t) = eiωmn t dt . (4.2.22)
0 i~

This is a key result and will be very useful in the applications we will consider.
Exercise: Prove the remarkable equality of transition probabilities

(1) (1)
Pm←n (t) = Pn←m (t) , (4.2.23)

valid to first order in perturbation theory.

It will also be useful to have our results in terms of the time-dependent coefficients cn (t)
introduced earlier through the expansion
X
Ψ(t)
e = cn (t)|ni . (4.2.24)
n

Since Ψ(0) = Ψ(0)

e the initial condition reads
X
Ψ(0) = e (0) (0) ,
cn (0)|ni = Ψ (4.2.25)
n

where we also used (4.2.9). In this notation, the cn (t) functions also have a λ expansion,
because we write X
e (k) (t) =
Ψ c(k)
n (t)|ni , k = 0, 1, 2, . . . (4.2.26)
n
84 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

and therefore the earlier relation

e (0) (t) e (1) (t) + λ2 Ψ

e (2) (t) + O λ3 .


Ψ(t)
e = Ψ +λ Ψ (4.2.27)

now gives
cn (t) = c(0) (1) 2 (2)
n (t) + λcn (t) + λ cn (t) + . . . (4.2.28)
e (0) (t)i is in fact constant we have
Since |Ψ

c(0) (0)
n (t) = cn (0) = cn (0) , (4.2.29)

where we used (4.2.25). The other initial conditions given earlier in (4.2.8) imply that

c(k)
n (0) = 0 , k = 1, 2, 3 . . . . (4.2.30)

e (1) (t) we have

Therefore, using our result (4.2.12) for Ψ

X Z t f 0)
δH(t X
e (1) (t) =
Ψ c(1)
n (t)|ni = dt0 cn (0)|ni , (4.2.31)
n 0 i~ n

and as a result,

XZ t f 0 )|ni
hm|δH(t
c(1)
m (t)
e (1) (t) =
≡ hm Ψ cn (0) dt0 . (4.2.32)
n 0 i~

We therefore have

XZ t
0 δHmn (t0 )
c(1)
m (t) = dt0 eiωmn t cn (0) . (4.2.33)
n 0 i~

The probability Pm (t) to be found in the state |mi at time t is

2
Pm (t) = |hm|Ψ(t)i|2 = hm|Ψ(t)i
e = |cm (t)|2 . (4.2.34)

To first order in perturbation theory the answer would be (with λ = 1)

(1) 2
Pm (t) = cm (0) + c(1)
m (t)
2
(4.2.35)
= cm (0) + cm (0)∗ c(1) (1) ∗ 2
m (t) + cm (t) cm (0) + O(δH ) .

(1)
Note that the |cm (t)|2 term cannot be kept to this order of approximation, since it is of
(2)
the same order as contributions that would arise from cm (t).
4.2. PERTURBATIVE SOLUTION 85

4.2.1 Example NMR

The Hamiltonian for a particle with a magnetic moment inside a magnetic field can be
written in the form
H = ω · S, (4.2.36)
where S is the spin operator and ω is precession angular velocity vector, itself a function
of the magnetic field. Note that the Hamiltonian has properly units of energy (ω~). Let us
take the unperturbed Hamiltonian to be

H (0) = ω0 Sz = ~
2 ω0 σz . (4.2.37)

For NMR applications one has ω0 ≈ 500 Hz and this represents the physics of a magnetic
field along the z axis. Let us now consider some possible perturbations.

Case 1: Time independent perturbation Let us consider adding at t = 0 a constant

perturbation associated with an additional small uniform magnetic field along the x axis:

H = H (0) + δH , with δH = ΩSx , (4.2.38)

For this to be a small perturbation we will take

Ω  ω0 . (4.2.39)

Hence, for the full Hamiltonian H we have ω = (Ω, 0, ω0 )

H = (Ω, 0, ω0 ) ·(Sx , Sy , Sz ) (4.2.40)

| {z }
ω

The problem is simple enough that an exact solution is possible. The perturbed Hamiltonian
ω
H has energy eigenstates |n; ±i, spin states that point with n = |ω| with energies ± ~2 |ω|.
These eigenstates could be recovered using time-independent non-degenerate perturbation
theory using Ω/ω0 as a small parameter and starting with the eigenstates |±i of H (0) .
In time-dependent perturbation theory we obtain the time-dependent evolution of initial
states as they are affected by the perturbation. Recalling (4.2.12) we have
Z t f 0
δH(t )
e (1) (t) =
Ψ Ψ(0) dt0 (4.2.41)
0 i~
86 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

The calculation of δH
f requires a bit of computation. One quickly finds that
h σz i h σz i  
δH(t)
f = exp iω0 t ΩŜx exp −iω0 t = Ω Ŝx cos ω0 t − Ŝy sin ω0 t . (4.2.42)
2 2
As a result we set:
Z t
e (1) (t) = Ω

Ψ Ŝx cos ω0 t0 − Ŝy sin ω0 t0 Ψ(0) dt0
i~ 0
1 Ω h
i
= Ŝx sin ω0 t + cos(ω0 t0 ) − 1 Ŝy Ψ(0) . (4.2.43)
i~ ω0
As expected, the result is first order in the small parameter Ω/ω0 . Following (4.2.16) the
time-dependent state is, to first approximation
!
h σz i 1 Ω h i
Ŝx sin ω0 t + cos(ω0 t0 ) − 1 Ŝy |Ψ(0)i


Ψ(t) = exp −iω0 t 1+
2 i~ ω0 (4.2.44)
+ O((Ω/ω0 )2 ) .

Physically the solution is clear. The original spin state Ψ(0) precesses about the direction
of ω with angular velocity ω.

Case 2: Time dependent perturbation. Suppose that to the original Hamiltonian we

add the effect of a rotating magnetic field, rotating with the same angular velocity ω0 that
corresponds to the Larmor frequency of the original Hamiltonian:
 
δH(t) = Ω Ŝx cos ω0 t + Ŝy sin ω0 t . (4.2.45)

To compute the perturbation δH f we can use (4.2.42) with t replaced by −t so that the
right-hand side of this equation is proportional to δH:
h σz i h σz i  
exp −iω0 t ΩŜx exp iω0 t = Ω Ŝx cos ω0 t + Ŝy sin ω0 t . (4.2.46)
2 2
Moving the exponentials on the left-hand side to the right-hand side we find
h σz i   h σz i
ΩŜx = exp iω0 t Ω Ŝx cos ω0 t + Ŝy sin ω0 t exp −iω0 t . (4.2.47)
2 2
The right-hand side is, by definition, δH.
f Thus we have shown that

δH(t)
f = ΩŜx , (4.2.48)

is in fact a time-independent Hamiltonian. This means that the Schrödinger equation for
Ψ
e is immediately solved
 f   
δHt e ΩŜx t
Ψ(t)
e = exp −i Ψ(0) = exp −i Ψ(0) . (4.2.49)
~ ~
4.3. FERMI’S GOLDEN RULE 87

The complete and exact answer is therefore

h iH (0) t i h σz i h σx i
Ψ(t) = exp − Ψ(t)
e = exp −iω0 t exp −iΩt Ψ(0) . (4.2.50)
~ 2 2

This is a much more non trivial motion! A spin originally aligned along ẑ will spiral into
the x, y plane with angular velocity Ω.

4.3 Fermi’s Golden Rule

Let us now consider transitions where the initial state is part of a discrete spectrum but the
final state is part of a continuum. The ionization of an atom is perhaps the most familiar
example: the initial state may be one of the discrete bound states of the atom while the
final state includes a free electron a momentum eigenstate that is part of a continuum of
non-normalizable states.
As we will see, while the probability of transition between discrete states exhibits pe-
riodic dependence in time, if the final state is part of a continuum an integral over final
states is needed and the result is a transition probability linear in time. To such probability
function we will be able to associate a transition rate. The final answer for the transition
rate is given by Fermi’s Golden Rule.
We will consider two different cases in full detail:

1. Constant perturbations. In this case the perturbation, called V turns on at t = 0 but

it is otherwise time independent:
(
H (0) , for t ≤ 0 ,
H = (4.3.1)
H (0) + V for t > 0 .

This situation is relevant for the phenomenon of auto-ionization, where an internal

transition in the atom is accompanied by the ejection of an electron.
88 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

2. Harmonic perturbations. In this case the time dependence of the perturbation δH is

periodic, namely,
H(t) = H (0) + δH(t) , (4.3.2)
with (
0, for t ≤ 0 ,
δH(t) = (4.3.3)
2H 0 cos ωt , for t > 0 .
Note the factor of two entering the definition of δH in terms of the time independent
H 0 . This situation is relevant to the interaction of electromagnetic fields with atoms.

Before starting with the analysis of these two cases let us consider the way to deal
with continuum states, as the final states in the transition will belong to a continuum.
The fact is that we need to be able to count the states in the continuuum, so we will
replace infinite space by a very large cubic box of side length L and we will impose periodic
boundary conditions on the wavefunctions. The result will be a discrete spectrum where
the separation between the states can be made arbitrarily small, thus simulating accurately
a continuum in the limit L → ∞. If the states are energetic enough and the potential is
short range, momentum eigenstates are a good representation of the continuum.
To count states use a large box, which can be taken to be a cube of side L:

We call L a regulator as it allows us to deal with infinite quantities (like the volume of
space or the number of continuum states). At the end of our calculations the value of L
must drop out. This is a consistency check. The momentum eigenstates ψ(x take the form
1
ψ(x) = √ eikx x eiky y eikz z , (4.3.4)
L3
with constant k = (kx , ky , kz ). It is clear that the states are normalized correctly
Z Z
1
|ψ(x)| d x = 3 d3 x = 1 .
2 3
(4.3.5)
box L
The k 0 s are quantized by the periodicity condition on the wavefunction:

ψ(x + L, y, z) = ψ(x, y + L, z) = ψ(x, y, z + L) = ψ(x, y, z) . (4.3.6)

The quantization gives

kx L = 2πnx → Ldkx = 2πdnx ,
ky L = 2πny → Ldky = 2πdny , (4.3.7)
kz L = 2πnz → Ldkz = 2πdnz .
4.3. FERMI’S GOLDEN RULE 89

Define ∆N as the total number of states within the little cubic volume element d3 k. It
follows from (4.3.7) that we have
 3
L
∆N ≡ dnx dny dnz = d3 k . (4.3.8)
2π
Note that ∆N only depends on d3 k and not on k itself: the density of states is constant in
momentum space.
Now let d3 k be a volume element determined in spherical coordinates k, θ, φ and by
ranges dk, dθ, dφ. Therefore

d3 k = k 2 dk sin θdθ dφ = k 2 dk dΩ (4.3.9)

We now want to express the density of states as a function of energy. For this we take
differentials of the relation between the wavenumber k and the energy E:
~2 k 2 m
E= → kdk = dE . (4.3.10)
2m ~2
Back in (4.3.9) we have
m
d3 k = k
dE dΩ , (4.3.11)
~2
hence  3
L m
∆N = k 2 dΩ dE . (4.3.12)
2π ~
We now equate
∆N = ρ(E)dE , (4.3.13)
where ρ(E) is a density of states, more precisely, it is the number of states per unit energy
at around energy E and with momentum pointing within the solid angle dΩ. The last two
equations determine for us this density:

L3 m
ρ(E) = k dΩ . (4.3.14)
8π 3 ~2

With a very large box, a sum over states can be replaced by an integral as follows
X Z
··· → · · · ρ(E)dE (4.3.15)
states
where the dots denote an arbitrary function of the momenta k of the states.
90 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

4.3.1 Constant transitions.

The Hamiltonian, as given in (4.3.1) takes the form
( (0)
H for t ≤ 0
H= (4.3.16)
H (0) + V for t > 0 .

We thus identify δH(t) = V for t ≥ 0. Recalling the formula (4.2.33) for transition ampli-
tudes to first order in perturbation theory we have
XZ t 0 Vmn
c(1)
m (t) = dt0 eiωmn t cn (0) . (4.3.17)
n 0 i~

To represent an initial state i at = 0 we take cn (0) = δn,i . For a transition to a final state
f at time t0 we set m = f and we have an integral that is easily performed:
0 t0
t0
Vf i eiωf i t
Z
(1) 1 iωf i t0 0
cf (t0 ) = Vf i e dt = (4.3.18)
i~ 0 i~ iωf i
0

Evaluating the limits and simplifying

Vf i   V eiωf i t0 /2 
ωf i t0

(1) iωf i t0 fi
cf (t0 ) = 1−e = (−2i) sin . (4.3.19)
Ef − Ei Ef − Ei 2
(1)
The transition probability to go from i at t = 0 to f at t = t0 is then |cf (t0 )|2 and is
therefore  
ω t
4 sin2 f2i 0
Pf ←i (t0 ) = |Vf i |2 . (4.3.20)
(Ef − Ei )2
This first order result in perturbation theory is expected to be accurate at time t0 if
Pf ←i (t0 )  1. Certainly a large transition probability at first order could not be trusted
and would require examination of higher orders.
To understand the main features of the result for the transition probability we examine
how it behaves for different values of the final energy Ef . If Ef 6= Ei the transition is said
to be energy non-conserving. Of course, energy is conserved overall, as it would be supplied
by the perturbation. If Ef = Ei we have an energy conserving transition. Both are possible
and let us consider them in turn.

1. Ef 6= Ei . In this case the transition probability Pf ←i (t0 ) as a function of t0 is shown

in Figure 4.2. The behavior is oscillatory with frequency |ωf i . If the amplitude of the
oscillation is much less than one
4|Vf i |2
1 (4.3.21)
(Ef − Ei )2
4.3. FERMI’S GOLDEN RULE 91

Figure 4.2: The transition probability as a function of time for constant perturbations.

then this first order transition probability Pf ←i (t0 ) is accurate for all times t0 as it is
always small. The amplitude is suppressed as |Ef − Ei | grows, due to the factor in
the denominator. This indicates that the larger the energy ‘violation’ the smaller the
probability of transition. This is happening because a perturbation that turns on and
then remains constant is not an efficient supply of energy.
2. Ef → Ei . In this limit ωf i approaches zero and therefore
(Ef − Ei )2 2
 
2 ωf i t0
sin ' t0 . (4.3.22)
2 4~2
It follows from (4.3.20) that
|Vf i |2 2
lim Pf ←i (t0 ) = t . (4.3.23)
Ef →Ei ~2 0
The probability for an energy-conserving transition grows quadratically in time, and
does so without bound! This result, however, can only be trusted for small enough t0
such that Pf ←i (t0 )  1.
Note that a quadratic growth of Pf ←i is also visible in the energy non-conserving Ef 6=
Ei case for very small times t0 . Indeed, (4.3.20) leads again to limt0 →0 Pf ←i (t0 ) =
|Vf i |2 t20 /~2 , while Ef 6= Ei . This behavior can be noted near the origin in Figure 4.2.
Our next step is to integrate the transition probability over the now discretized contin-
uum of final states. Remarkably, upon integration the oscillatory and quadratic behaviors
of the transition probability as a function of time will conspire to create a linear behavior!
The sum of transition probabilities over final states is approximated by an integral, as
explained in (4.3.15). We thus have
 
ω t
X Z Z sin2 f2i 0
Pf ←i (t0 ) = Pf ←i (t0 )ρ(Ef )dEf = 4 |Vf i |2 ρ(Ef )dEf . (4.3.24)
(Ef − Ei )2
f
92 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

We have noted that Pf ←i in the above integrand is suppressed as |Ef − Ei | becomes large.
We therefore expect that the bulk of the contribution to the integral will occur for a narrow
range ∆Ef of Ef near Ei . Let us assume now that |Vf i |2 and ρ(Ef ) are slow varying
and therefore approximately constant over the narrow interval Ef (we will re-examine this
assumption below). If this is the case we can evaluate them for Ef set equal to Ei and take
them out of the integrand to find
X 4|Vf i |2
Pf ←i (t0 ) = ρ(Ef = Ei ) · I(t0 ) , (4.3.25)
~2
f

where the integral I(t0 ) is given by

Z   Z  
1 2 ωf i t0 2 ωf i t0 dωf i
I(t0 ) ≡ 2 sin dE f = ~ sin . (4.3.26)
ωf i 2 2 ωf2i

As it stands, the integral extends from minus infinity to plus infinity. It is useful to plot the
final integrand for I(t0 ) as a function of the integration variable ωf i . The result is shown
in Figure 4.3 and exhibits a main central lobe followed by symmetrically arranged lobes of
decreasing amplitude. The lobes are separated by zeroes occurring for ωf i = 2πk/t0 , with
k integer. Note that for

 
ωf i t0
Figure 4.3: Plot of 1
ωf2 i
sin2 2 , the integrand of I.

The largest contribution to I(t0 ) arises from the main lobe

2π 2π
− < ωf i < . (4.3.27)
t0 t0
In terms of energies this corresponds to the range
2π~ 2π~
Ei − < Ef < Ei + . (4.3.28)
t0 t0
4.3. FERMI’S GOLDEN RULE 93

We need this range to be a narrow, thus t0 must be sufficiently large. The narrowness
is required to justify our taking of the density of states ρ(E) and the matrix element |Vf i |2
out of the integral. If we want to include more lobes this is can be made consistent with a
narrow range of energies by making t0 larger.
The linear dependence of I(t0 ) as a function of t0 is intuitively appreciated by noticing
that the height of the main lobe is proportional to t20 and its width is proportional to 1/t0 .
In fact, the linear dependence is a simple mathematical fact made manifest by a change of
variables. Letting
ωf i t0 t0
u= =⇒ du = dωf i , (4.3.29)
2 2
so that
2~ ∞ sin2 u ~t0 ∞ sin2 u
Z Z
I(t0 ) = = , (4.3.30)
t0 −∞ u2 · t42 2 −∞ u2
0

making the linear dependence in t0 manifest. The remaining integral evaluates to π and we
thus get
I(t0 ) = π2 ~t0 . (4.3.31)
Had restricted the integral to the main lobe, concerned that the density of states and matrix
elements would vary over larger ranges, we would have gotten 90% of the total contribution.
Including the next two lobes, one to the left and one to the right, brings the result up to
95% of the total contribution. By the time we include ten or more lobes on each side we
are getting 99% of the answer. For sufficiently large t0 is is still a narrow range.
Having determined the value of the integral I(t0 ) we can substitute back into our ex-
pression for the transition probability (4.3.26). Replacing t0 by t
X 4|Vf i |2 π 2π
Pk←i (t) = ρ(Ef ) ~t = |Vf i |2 ρ(Ef ) t . (4.3.32)
~2 2 ~
k

This holds, as discussed before, for sufficiently large t. Of course t cannot be too large as it
would make the transition probability large and unreliable. The linear dependence of the
transition probability implies we can define a transition rate w, or probability of transition
per unit time, by dividing the transition probability by t:
1X
w≡ Pf ←i (t) . (4.3.33)
t
f

This finally gives us Fermi’s golden rule for constant perturbations:

2π
Fermi’s golden rule: w = |Vf i |2 ρ(Ef ) , Ef = Ei . (4.3.34)
~

Not only is the density of states evaluated at the energy Ei , the matrix element Vf i is also
evaluated at the energy Ei and other observables of the final state, like the momentum. In
94 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

this version of the golden rule the integration over final states has been performed. The
units are manifestly right: |Vf i |2 has units of energy squared, ρ has units of one over energy,
and with an ~ in the denominator the whole expression has units of one over time, as
appropriate for a rate. We can also see that the dependence of w on the size-of-the-box
regulator L disappears: The matrix element

Vf i = hf |V |ii ∼ L−3/2 , (4.3.35)

because the final state wavefunction has such dependence (see (4.3.4)). Then the L depen-
dence in |Vf i |2 ∼ L−3 cancels with the L dependence of the density of states ρ ∼ L3 , noted
in (4.3.14).
Let us summarize the approximations used to derive the golden rule. We have two
conditions that must hold simultaneously:

1. We assumed that t0 is large enough so that the energy range

2π~ 2π~
Ei − k < Ef < Ei + k , (4.3.36)
t0 t0

with k some small integer, is narrow enough that ρ(E) and |Vf i |2 are approximately
constant over this range. This allowed us to take them out of the integral simplifying
greatly the problem and making a complete evaluation possible.

2. We cannot allow t0 to be arbitrarily large. As we have

X
Pf ←i (t0 ) = w t0 , (4.3.37)
f

we must keep wt0  1 for our first order calculation to be accurate.

Can the two conditions on t0 be satisfied? There is no problem if the perturbation can
be made small enough: indeed, suppose condition 1 is satisfied for some suitable t0 but
condition 2 is not. Then we can make the perturbation V smaller making w small enough
that the second condition is satisfied. In practice, in specific problems, one could do the
following check. First compute w assuming the golden rule. Then fix t0 such that wt0 is
very small, say equal to 0.01. Then check that over the range ∼ ~/t0 the density of states
and the matrix elements are roughly constant. If this works out the approximation should
be very good!

Helium atom and autoionization. The helium has two protons (Z = 2) and two
electrons. Let H (0) be the Hamiltonian for this system ignoring the the Coulomb repulsion
between the electrons:
p21 e2 p2 e2
H (0) = − + 2 − . (4.3.38)
2m r1 2m r2
4.3. FERMI’S GOLDEN RULE 95

Here the labels 1 and 2 refer to each one of the two electrons. The spectrum of this
Hamiltonian consists of hydrogenic states, with n1 , n2 the principal quantum numbers for
the electrons. The energies are then
   
2 1 1 1 1
En1 ,n2 = −(13.6 eV)Z + = −(54.4 eV) + . (4.3.39)
n21 n22 n21 n22

Figure 4.4: Hydrogenic states in helium and continuum states of negative total energy.

For the hydrogen atom we have bound states of negative energy and continuum states
of positive energy that can be described to a good approximation as momentum eigenstates
of the electron which is no longer bound to the proton. Since we have two electrons in the
case of helium, there are continuum states in the spectrum with negative energy.
This first happens for n1 = 1 in the limit as n2 → ∞. For n1 = 1 and n2 = ∞ the
second electron is essentially free and contributes no energy. Thus a continuum appears for
energy E1,∞ = −54.4eV. This (1S)(∞) continuum extends for all E ≥ −54.4eV as the free
electron can have arbitrary positive kinetic energy. The state (2S)(∞) is the beginning of
a second continuum, also including states of negative energy. In general the state (nS)(∞)
with n ≥ 1 marks the beginning of the n-th continuum. In each of these continua one
electron is still bound and the other is free. A diagram showing some discrete states and a
couple of continua is given in Figure 4.4.
Self-ionizing energy-conserving transitions can occur because discrete states can find
themselves in the middle of a continuum. The state (2S)2 , for example, with two electrons
on the 2S configuration and with energy E2,2 = −27eV is in the middle of the (1S)(∞)
continuum. We can view the original (2S)2 hydrogenic state as a t = 0 eigenstate of H (0)
and treat the Coulomb repulsion as a perturbation. We thus have a total Hamiltonian H
96 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

that takes the form

e2
H = H (0) + V , V = . (4.3.40)
|r1 − r2 |
The perturbation V produces “auto-ionizing” Auger transitions to the continuum. We have
a transition from a state with energy E2,2 = −27eV to a state of one bound electron with
energy −54.4eV and one free electron with kinetic energy of 27eV. That final state is part
of a continuum. Radiative transitions from (2S)2 to 1S2S, with photo-emission, are in fact
a lot less likely than auto-ionizing transitions!
We will not do the quantitative analysis required to determine lifetime of the (2S)2 state.
In general auto-ionization is a process in which an atom or a molecule in an excited state
spontaneously emits one of the outer-shell electrons. Auto-ionizing states are in general
short lived. Auger transitions are auto-ionization processes in which the filling of an inner
shell vacancy is accompanied by the emission of an electron. Our example of the (2S)2
state is an Auger transition. Molecules can have auto ionizing Rydberg states, in which the
little energy needed to remove the Rydberg electron is supplied by a vibrational excitation
of the molecule.

4.3.2 Harmonic Perturbation

It is now time to consider the case when the perturbation is harmonic. We will be able
to derive a similar looking Fermi golden rule for the transition rate. The most important
difference is that now the transitions are of two types. They involve either absorption of
energy or a release of energy. In both cases that energy (absorbed or released) is equal to
~ω where ω is the frequency of the perturbation.
As indicated in (4.3.3) we have

H(t) = H (0) + δH(t) , (4.3.41)

where the perturbation δH(t) takes the form

(
0, for t ≤ 0 ,
δH(t) = (4.3.42)
2H 0 cos ωt , for t > 0 .

Here ω > 0 and H 0 is some time independent Hamiltonian. The inclusion of an extra factor
of two in the relation between δH and H 0 is convenient because it results in a golden rule
does not have additional factors of two compared to the case of constant transitions.
We again consider transitions from an initial state i to a final state f . The transition
amplitude this time From (4.2.33)
Z t0
(1) 1 0
cf (t) ) = dt0 eiωf i t δHf i (t0 ) . (4.3.43)
i~ 0
4.3. FERMI’S GOLDEN RULE 97

Using the explicit form of δH the integral can be done explicitly

1 t0 iωf i t0
Z
(1)
cf (t0 ) = e 2Hf0 i cos ωt0 dt0
i~ 0
Hf0 i t0  i(ω +ω)t0
Z 
0
= e fi + ei(ωf i −ω)t dt0 (4.3.44)
i~ 0
" #
Hf0 i ei(ωf i +ω)t0 − 1 ei(ωf i −ω)t0 − 1
=− + .
~ ωf i + ω ωf i − ω

Comments:

• The amplitude takes the form of a factor multiplying the sum of two terms, each one a
fraction. As t0 → 0 each fraction goes to it0 . For finite t0 , which is our case of interest,
each numerator is a complex number of bounded absolute value that oscillates in time
from zero up to two. In comparing the two terms the relevant one is the one with the
smallest denominator.1

• The first term is relevant as ωf i + ω ≈ 0, that is, when there are states at energy
Ef = Ei − ~ω. This is “stimulated emission”, the source has stimulated a transition
in which energy ~ω is released.

• The second term relevant if ωf i − ω ≈ 0, that is, when there are states at energy
Ef = Ei + ~ω. Energy is transferred from the perturbation to the system, and we
have a process of “absorption”.

Both cases are of interest. Let us do the calculations for the case of absorption; the
answer for the case of spontaneous emission will be completely analogous. We take i to be
a discrete state, possibly bound, and f to be a state in the continuum at the higher energy
Ef ≈ Ei + ~ω. Since ωf i ' ω, the second term in the last line of (4.3.44) is much more
important than the first. Keeping only the second term we have
i
Hf0 i e 2 (ωf i −ω)t0
 
(1) ωf i − ω
cf (t0 ) = − 2i sin t0 , (4.3.45)
~ ωf i − ω 2

and the transition probability is

 
ωf i −ω
4|Hf0 i |2 sin2 2 t0
(1)
Pf ←i (t0 ) = |cf (t0 )|2 = (4.3.46)
~2 (ωf i − ω)2

The transition probability is exactly the same as that for constant perturbations (see
(4.3.20)) with V replaced by H 0 and ωf i replaced by ωf i − ω. The analysis that follows is
1
This is like comparing two waves that are being superposed. The one with larger amplitude is more
relevant even though at some special times, as it crosses the value of zero, it is smaller than the other wave.
98 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

completely analogous to the previous one so we shall be brief. Summing over final states
we have
 
2 ωf i −ω
4|Hf0 i |2 sin t
Z Z 0
X 2
Pk←i (t0 ) = Pf ←i ρ(Ef )dEf = 2
ρ(Ef )dEf . (4.3.47)
~ (ωf i − ω)2
k

This time the main contribution comes from the region

2π 2π
− < ωf i − ω < (4.3.48)
t0 t0
In terms of the final energy this is the band

2π~ 2π~
Ei + ~ω − < Ef < Ei + ~ω + (4.3.49)
t0 t0
For sufficiently large t0 this is the narrow band of states illustrated in Figure 4.5. Assume

Figure 4.5: In the absorption process we must integrate over a narrow band of states about
the final energy Ei + ~ω.

that over the band Hf0 i and the density of states is constant so that we get
 
Z sin2 ωf i −ω
X 4 0 2 2 t0
Pk←i (t0 ) = |H | ρ(Ei + ~ω) dωf i . (4.3.50)
~ fi (ωf i − ω)2
k

Defining
1
u≡ 2 (ωf i − ω) t0 → du = 12 dωf i t0 , (4.3.51)
the integral in (4.3.50) becomes
∞ ∞
sin2 u 2 sin2 u
Z Z
t0 t0
 2 du = 2
du = π. (4.3.52)
−∞ 2u t0 2 −∞ u 2
t0
4.4. IONIZATION OF HYDROGEN 99

Finally, the transition probability is

X 2π 0 2
Pk←i (t0 ) = |Hf i | ρ(Ei + ~ω) t0 . (4.3.53)
~
k

The transition rate w is finally given by

2π
Fermi’s golden rule: w = ρ(Ef )|Hf0 i |2 , Ef = Ei + ~ω . (4.3.54)
~

Here H 0 (t) = 2H 0 cos ωt. Equation (4.3.54) is known as Fermi’s golden rule for the case of
harmonic perturbations. For the case of spontaneous emission the only change required in
the above formula is Ef = Ei − ~ω.

4.4 Ionization of hydrogen

We aim to find the ionization rate for hydrogen when hit by the harmonically varying
electric field of an electromagnetic wave. We assume the hydrogen atom has its electron
on the ground state. In this ionization process a photon ejects the bound electron, which
becomes free.
Let us first do a few estimates to understand the validity of the approximations that will
be required. If the electromagnetic field has frequency ω the incident photons have energy
Eγ = ~ω . (4.4.1)
The energy Ee and the magnitude k of the momentum of the ejected electron are given by
~2 k 2
Ee = = Eγ − Ry , (4.4.2)
2m
where the Rydberg Ry is the magnitude of the energy of the ground state:
e2 ~2 ~c
2Ry = = 2 =α , Ry ' 13.6 eV . (4.4.3)
a0 ma0 a0

Inequalities
1. Any electromagnetic wave has spatial dependence. We can ignore the spatial depen-
dence of the wave if the wavelength λ of the photon is much bigger than the Bohr
radius a0 :
λ
 1. (4.4.4)
a0
Such a condition puts an upper bound on the photon energy, since the more energetic
photon the smaller its wavelength. To bound the energy we first write
2π 2πc 2π~c
λ= = = , (4.4.5)
kγ ω ~ω
100 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

and then find

λ 2π ~c 4π Ry Ry
= = ' 1722 (4.4.6)
a0 ~ω a0 α ~ω ~ω

The inequality (4.4.4) then gives

~ω  1722 Ry ' 23 keV (4.4.7)

2. For final states we would like to use free particle momentum eigenstates. This requires
the ejected electron to be energetic enough not to be much effected by the Coulomb
field. As a result, the photon to be energetic enough, and this constraint provides a
lower bound for its energy. We have

Ee = Eγ − Ry  Ry → ~ω  Ry . (4.4.8)

The two inequalities above imply

Ry  ~ω  1722 Ry . (4.4.9)

If consider that 1  10 we could take

140eV ≤ ~ω ≤ 2.3 keV . (4.4.10)

Note that even for the upper limit the electron is non relativistic: 2.3 keV  me c2 ' 511keV.
Exercise: Determine ka0 in terms of ~ω and Ry .
Solution:
~2 k 2 ~2
   
~ω ~ω
= ~ω − Ry = Ry −1 = −1 (4.4.11)
2m Ry 2ma20 Ry
s
~ω ~ω
k 2 a20 = − 1 → ka0 = − 1. (4.4.12)
Ry Ry
This is the desired result. In the range of (4.4.10) we have

3 ≤ ka0 ≤ 13 . (4.4.13)

Calculating the matrix element. Our perturbation Hamiltonian is

δH = −eΦ , (4.4.14)

where Φ is the electric scalar potential. Let the electric field at the atom be polarized in
the ẑ direction
E(t) = E(t)ẑ = 2E0 cos ωt ẑ (4.4.15)
4.4. IONIZATION OF HYDROGEN 101

The associated scalar potential is

Φ = −E(t)z , (4.4.16)
and therefore
δH = eE(t)z = eE(t)r cos θ = 2 eE0 r cos θ cos ωt ≡ 2H 0 cos ωt (4.4.17)
| {z }
H0

We have thus identified, in our notation,

H 0 = eE0 r cos θ . (4.4.18)
We want to compute the matrix element between an initial state |ii that is the ground state
of hydrogen, and a final state |f i which is an electron plane wave with momentum ke . The
associated wavefunctions are
1
Final state: uk (x) = 3/2 eik·r (4.4.19)
L
1 − r
Initial state: ψ0 (r) = p 3 e a0 (4.4.20)
πa0
The only physical angle here is that between the ejected electron momentum ke and the
electric field polarization E. We expect electron to be ejected maximally along E. This
suggests rearranging the axes to have the electron momentum along the z axis and and
letting θ be the angle between the electron momentum and the electric field. The integration
variable r will have angles θ0 , φ0 , and the angle between the electric field and r is now called
θ00 as shown in the figure, so that H 0 = eE0 r cos θ00 :
Z
1 1 − r
hf |H |ii = d3 x 3/2 eik·r eE0 r cos θ00 p 3 e a0
0
L πa0
Z
eE0 0 − r
=p 3 r2 dr sin θ0 dθ0 dφ0 eikr cos θ r cos θ00 e a0 (4.4.21)
πa0 L3
102 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

The main complication with doing the integral is the factor cos θ00 . The dot product of unit
vectors along E and n is cos θ00 :
cos θ00 = (sin θ cos φ)(sin θ0 cos φ0 ) + (sin θ sin φ)(sin θ0 sin φ0 ) + cos θ cos θ0
= sin θ sin θ0 cos(φ − φ0 ) + cos θ cos θ0 (4.4.22)
Since the following integral vanishes
Z
dφ0 cos(φ − φ0 ) = 0 (4.4.23)

the first term in the expression for cos θ00 will vanish upon φ0 integration. We therefore can
replace cos θ00 → cos θ cos θ0 to find
Z
eE0 0 − r
hf |H 0 |ii = p 3 r3 dr sin θ0 dθ0 dφ0 eikr cos θ cos θ cos θ0 e a0
πa0 L3
Z Z 1
eE0 − ar 0
= p 3 (cos θ)(2π) r dr e 3 0 d(cos θ0 ) cos θ0 eikr cos θ (4.4.24)
πa0 L3 −1

Now let r = a0 u and do the radial integration:

Z 1 Z
0 eE0 0 0 0
hf |H |ii = p 3 2π cos θa0 4
d(cos θ ) cos θ u3 du e−u(1+ika0 cos θ )
πa0 L3 −1
Z 1
eE0 3!
= p 3 2π cos θa40 d(cos θ0 ) cos θ0 . (4.4.25)
πa0 L3 −1 (1 + ika0 cos θ0 )4

Writing x = cos θ0 the angular integral is not complicated:

Z 1
eE0 3! x
hf |H 0 |ii = p 3 2π cos θa40 4 4 dx
3 (ika )

πa0 L 0 −1 x + 1
ika0
 
1
eE0 3! 8 ika 0
=p 3 2π cos θa40 4  3
πa0 L3 (ika )
0
3 1 + k21a2
0

32πeE0 a0 ka40
= −i p 3 cos θ (4.4.26)
πa0 L3 (1 + k 2 a20 )3
Hence, with a little rearrangement

√ ka4 1
hf |H 0 |ii = −i32 π (eE0 a0 ) p 30 cos θ . (4.4.27)
a0 L (1 + k 2 a20 )3
3

The above matrix element has the units of (eE0 a), which is energy. This is as expected.
Squaring we find
k 2 a5 cos2 θ
|Hf0 i |2 = 1024 π (eE0 a)2 30 (4.4.28)
L (1 + k 2 a20 )6
4.4. IONIZATION OF HYDROGEN 103

At this point, with θ the angle between ke and E, it is more convenient to align E along
the z-axis and let ke be defined by the polar angles θ, φ. The density of states was given in
(4.3.14)

L3 m
ρ(Ee ) = k dΩ (4.4.29)
8π 3 ~2

so that using Fermi’s Golden rule, the rate dw to go into final states in the solid angle dΩ
is
2π
dw = ρ(Ee )|Hf0 i |2
~
2π L3 m 2 5
2 k a0 cos2 θ
= k dΩ 1024π(eE 0 a 0 ) . (4.4.30)
~ 8π 3 ~2 L3 (1 + k 2 a20 )6
It follows that
dw 256 ma20 (eE0 a0 )2 k 3 a30
= cos2 θ . (4.4.31)
dΩ π ~2 ~ (1 + k 2 a20 )6
dw
dΩ is the probability of ionization per unit time and per unit solid angle. All the ejected
electrons will have the same momentum ~k. Note that the units have worked out: w ∼
[E]2 1 1
~ · [E] ∼ T as expected. In here 2E0 is the peak amplitude of the electric field in the
wave. The cos2 θ implies that the electron tends to be ejected in the direction of the electric
field.
The total ionization probability per unit time is obtained by integration over solid angle.
Using Z
cos2 θ dΩ = 1
3 4π , (4.4.32)
~2
and recalling that ma20
= 2Ry

512 (eE0 a0 )2 k 3 a30

Z
dw
w= dΩ = . (4.4.33)
dΩ 3 ~Ry (1 + k 2 a20 )6
For the window of validity (4.4.13) we have 9 ≤ (ka0 )2 ≤ 169, and we neglect the “one” in
the denominator to get
512 (eE0 a0 )2 1
w = . (4.4.34)
3 ~Ry (ka0 )9
This is our final answer. For numerical calculations it is useful to note the atomic units in
which the answer takes the form
256  Ep 2 1 1
w = . (4.4.35)
3 E∗ t∗ (ka0 )9
104 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

Here Ep = 2E0 is the peak amplitude of the electric field. Moreover, the atomic electric
field E∗ and the atomic time t∗ are given by

2Ry e
E∗ = = 2 = 5.14 × 1011 V/m
ea0 a0 (4.4.36)
a0
t∗ = = 2.42 × 10−17 sec.
αc
Note that E∗ is the electric field of a proton at a distance a0 while t∗ is the time it takes
the electron to travel a distance a0 at the velocity αc in the ground state. A laser intensity
of 3.55 × 1016 W/cm2 has an peak electric field of magnitude E∗ .

4.5 Light and atoms

4.5.1 Absorption and stimulated emission
The physical problem we are trying to solve consists of a collection of atoms with two
possible energy levels interacting with light at a temperature T . We want to understand
the processes of absorption and emission of radiation and how they can produce thermal
equilibrium.
Let us first consider a single atom and the possible processes. Consider two possible
levels of an electron in an atom

Define
Eb − Ea
ωab ≡ .
~
Imagine now shining light into the atom at a frequency ωab . There are two possibilities
depending on the initial state of the atom:

(i) Electron initially in |ai: there will be an absorption rate at which a photon is absorbed
and the electron goes from |ai → |bi.

(ii) Electron initially in |bi: there will be a stimulated emission rate at which the photon
field stimulates an electronic transition |bi → |ai with the release of an additional
photon.
 4.5. LIGHT AND ATOMS 105

These processes are illustrated in the figure below:

A LASER, Light Amplification by Stimulated Emission of Radiation, works by having pop-

ulation inversion, namely most of the atoms are in the excited energy level. Then any small
number of photons can trigger larger and larger numbers of stimulated emission processes!

4.5.2 Einstein’s Argument

Atoms in states a or b with Eb > Ea , with populations Na and
Nb respectively. The atoms are in equilibrium with a bath of
photons all at temperature T . Einstein discovered a number
of relations from the condition of equilibrium.
Fact 1: Equilibrium values for populations:

Ṅa = Ṅb = 0 (4.5.1)

Fact 2: Equilibrium populations governed by thermal distribu-

tion
Na e−βEb 1
= −βEa = e−β~ωab , β≡ (4.5.2)
Nb e kb T
 106 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

Fact 3: For a thermal blackbody, the energy U (ω)dω per unit

volume in the frequency range dω is known to be

~ ω 3 dω
U (ω)dω = (4.5.3)
π 2 c3 eβ~ω − 1

Process Rate
Absorption: |ai → |bi Bab U (ωba )Na
photon absorbed
Stimulated emission: |bi → |ai Bba U (ωba )Nb
photon released

In the table above we have indicated the two obvious processes: absorption and stim-
ulated emission. The rate indicated is the number of transitions per unit time. For ab-
sorption, this rate is proportional to the number Na of atoms in the ground state, capable
of absorbing a photon, times U (ωab ) which captures the information about the number of
photons available, times a B coefficient Bab that we want to determine. For stimulated
emission, the rate is proportional to the number Nb of atoms in the excited state, thus
capable of emitting a photon, times U (ωab ) times a B coefficient Bba . The inclusion of
U (ωab ) reflects the “stimulated” character of the transition.
Can we make this work, that is, can we achieve equilibrium? We will see that we cannot.
With the two processes above, the rate of change of Nb is

Ṅb = rate absorption − rate stimulated emission (4.5.4)

At equilibrium Ṅb = 0, hence

0 = Ṅb = Bab U (ωba )Na − Bba U (ωba )Nb

= (Bab Na − Bba Nb )U (ωba )
 
0 = Na Bab − Bba e−β~ωba U (ωba ) (4.5.5)

This is a strange result: in order to have equilibrium we need Bab − Bba e−β~ωba = 0. The
B coefficients, however, depend on the electronic configurations in the atom and not on
the temperature T . Thus this cancellation is not possible for arbitrary temperature. We
also note that the photon energy density does not feature in the equilibrium condition. In
conclusion, equilibrium is not possible.
What are we missing? Another process: spontaneous emission!!, an emission rate that
does not depend on the thermal photons. The rate is proportional to the number of atoms
Nb in the excited state, with a coefficient of proportionality called A:
4.5. LIGHT AND ATOMS 107

Process Rate
Spontaneous emission: |bi → |ai ANb
photon released

Reconsider now the equilibrium condition with this extra contribution to Ṅb :

0 = Ṅb = Bab U (ωba )Na − Bba U (ωba )Nb − ANb

 
Na
=⇒ A = Bab − Bba U (ωba )
Nb
A 1
=⇒ U (ωba ) = (4.5.6)
Bab eβ~ωba − BB
ba
ab

The equilibrium condition indeed gives some important constraint on U (ωab ). But from Eq.
(4.5.3) we know
~ ω3 1
U (ωba ) = 2 ba3 β~ω (4.5.7)
π c e ba − 1
Hence comparing the two equations we get

A ~ω 3
Bab = Bba and = 2 ba3 (4.5.8)
Bab π c

As we’ll see, we’ll be able to calculate Bab , but A is harder. Happily, thanks to (4.5.8), we
can obtain A from Bab .

Spontaneous emission does not care about U (ωba ); the photons flying around. At a
deep level one can think of spontaneous emission as stimulated emission due to vacuum
fluctuation of the EM field.

For a given atomic transition expect stimulated emission rate to dominate at higher
temperature, the there are more photons around. Spontaneous emission should dominate
at very low temperature. Indeed from (4.5.6)

 
A ~ ωba
= exp −1
Bab U (ωba ) kb T
108 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

4.5.3 Atom/light interaction

~ field. Effects of B
~ are weaker by O v ∼ α. For optical frequencies λ ∼


Focus on E c
4000 − 8000 Å and since a0 ' 0.5 Å, we can ignore the spatial dependence of the field (even
for ionization frequencies aλ0 ∼ 1700)
Electric field at the atom

E(t) = E(t)n = 2E0 cos(ωt)n

where n is the direction of the field.

Φ(r, t) = −r · E(t) , ∇Φ = −E (4.5.9)

as expected. The perturbation is therefore

δH = +qΦ(r) = −qr · E(t) (4.5.10)

By defining the dipole moment d as d ≡ qr, we can rewrite the perturbation as

δH = −d · E(t) = −d · n2E0 cos(ωt) = 2(−d · nE0 ) cos(ωt) . (4.5.11)

Since we defined δH = 2H 0 cos ωt we can read

H 0 = −d · n E0 . (4.5.12)

Recall that to first order in perturbation theory Pb←a (t) = Pa←b (t) so let’s consider just
Pa←b (t), the stimulated emission process, from (4.3.46)
0 |2 sin2 ωba −ω t ω −ω
4E02 |(d · n)ab |2 sin2 ba2 t



4|Hab 2
Pa←b (t) = = (4.5.13)
~2 (ωba − ω)2 ~2 (ωba − ω)2

Now think in terms of energy. The energy density uE in the electric field E(t) = 2E0 cos(ωt)n
is
|E(t)|2 4E02 4E02 1 E2
uE = = cos2 ωt =⇒ huE itime = · = 0. (4.5.14)
8π 8π 8π 2 4π
In a wave the electric and magnetic energy are the same and therefore

E02
huitime = 2huE itime = =⇒ E02 = 2πhui (4.5.15)
2π
4.5. LIGHT AND ATOMS 109

The superposition of light is incoherent, so we will add probabilities of transition due to

each component of light. For this we must turn a sum of electric field intensities into an
integral.

X Z
E02 (ωi ) = 2π U (ω)dω (4.5.16)
i

where U (ω) is the energy density per unit frequency. In this way the transition rate in
terms of energy reads

sin2 ωba2−ω t


|(d · n)ab |2
Z
Pa←b (t) = 2π U (ω)dω
~2 (ωba − ω)2

sin2 ωba2−ω t


|(d · n)ab |2
Z
= (2π)U (ωab ) dω (4.5.17)
~2 (ωba − ω)2

As usual, take x ≡ ωba2−ω t =⇒ dω = 2 dx

t , so that (4.5.17) is

sin2 x
Z
2 2
·t dx = 2tπ (4.5.18)
t x2

4π 2
Ra←b = |(d · n)ab |2 U (ωba ) (4.5.19)
~2
So far we have two vectors: d which depends on the atom geometry and n which is the
direction of the electric field. Since light comes in all possible polarization, this amounts to
averaging over all possible directions of n
D E D X ∗  X E
2
djab nj (diab )∗ (djab )hni nj i
2
X X
|dab · n| = diab ni = diab ni =
i i j i,j
(4.5.20)
Expect
hnx nx i = hny ny i = hnz nz i (4.5.21)
Since DX E
ni ni = hn2 i = 1 (4.5.22)
i

then
1
hni nj i = δij (4.5.23)
3
110 CHAPTER 4. TIME DEPENDENT PERTURBATION THEORY

D E 1 1
|dab · n|2 = d∗ab · dab ≡ |dab |2 (4.5.24)
3 3
This is the magnitude of a complex vector!

4π 2
Ra←b = |dab |2 U (ωba ) (4.5.25)
3~2

This is the transition probability per unit time for a single atom

4π 2
Bab = |dab |2 (4.5.26)
3~2
thus recalling (4.5.8)
3 3
~ωba ~ωba 4π 2
2
A=3
B ab = |dab |2 (4.5.27)
π c π c 3~2
2 3

hence we have that A, the transition probability per unit time for an atom to go from
|bi → |ai, is
3
4 ωba
A = |dab |2 . (4.5.28)
3 ~c3

1
The lifetime for the state is τ = A. The number N of particles decays exponentially in time

dN
= −AN =⇒ N (t) = e−At = N0 e−t/τ (4.5.29)
dt
If there are various decay possibilities A1 , A2 , . . . , the transition rates add
1
Atot. = A1 + A2 + . . . and τ= (4.5.30)
Atot.

4.5.4 Selection rules

(to be covered in recitation) Given two states |n`mi and |n0 `0 m0 i, when hn`m|r|n0 `0 m0 i =
6 0?
One can learn that

hn`m|z|n0 `0 m0 i = 0 for m0 6= m (4.5.31)

0 0 0 0 0 0 0
hn`m|x|n ` m i = hn`m|y|n ` m i = 0 for m 6= m ± 1 (4.5.32)

Hence no transition unless

∆m ≡ m0 − m = 0, ±1 (4.5.33)
Additionally
∆` ≡ `0 − ` = ±1 (4.5.34)
MIT OpenCourseWare
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8.06 Quantum Physics III

Spring 2018

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 Chapter 6: Adiabatic approximation

B. Zwiebach
June 2, 2017

Contents
1 Introduction 1
1.1 Adiabatic approximation in Classical Mechanics . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Quantum mechanics systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2 Adiabatic Evolution 5

3 Systematic approach 7

4 Landau-Zener transitions 9

5 Berry’s phase 12

6 Molecules and Born-Oppenheimer 15

6.1 Born-Oppenheimer approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6.2 Following the direct route . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6.3 The H2+ ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

1 Introduction
1.1 Adiabatic approximation in Classical Mechanics
Let’s go back to classical mechanics, with a harmonic oscillator performing motion but with ω(t) not
constant. The hamiltonian of the system would be

p2 1
H(x, p, ω(t)) = + mω 2 (t)x2 (1.1)
2m 2
where x and p are going to be functions of time.
In general
dH ∂H ∂H ∂H
= ẋ + ṗ + . (1.2)
dt ∂x ∂p ∂t
Hamilton’s equation of motion read
∂H ∂H
= x˙ , = −p˙ . (1.3)
∂p ∂x

1
Even if you are not familiar with these, you probably know well their quantum analogs:
   
d hxi ∂H d hxi ∂H
i~ = h[x, H]i = i~ → =
dt ∂p dt ∂p
   
d hpi ∂H d hpi ∂H
i~ = h[p, H]i = −i~ → =−
dt ∂x dt ∂x
(1.4)

At any rate, equations (1.3) imply that the first two terms in the right-hand side of (1.2) vanish and
we have
dH ∂H
= ˙ 2.
= mω ωx (1.5)
dt ∂t
We have an adiabatic change if the time scale τ for change is much greater than time scale of the
2π
oscillation, T = ω(t) .

What remains roughly constant as ω(t) changes adiabatically?

H(t)
Claim: I(t) ≡ is almost constant in adiabatic changes of ω. (1.6)
ω(t)
I(t) is called the adiabatic invariant.
Let us see why this is so:
 2  
dI 1  dH  1  � 2

p 1 2 2
= 2 ω − H(t)ω˙ = 2 ω mω ωx ˙ − + mω (t)x ω̇ =
dt ω dt ω 2m 2
p2
 
ω̇ 1 2 2 ω̇
= 2 2 mω (t)x − = 2 (V (t) − K(t)) , (1.7)
ω 2m ω
where V and K are the potential and kinetic energies, respectively. We want to understand why this
right-hand side is small. Clearly, ωω̇2 is slowly varying if ω̇ is slowly varying, but the term in parenthesis
is actually quickly varying. Indeed, with

x = A sin ωt and p = Amω cos ωt

then the parenthesis goes like

p2
 
2 2
1
2 mω x − 2m ∼ 21 mω 2 (sin2 ωt − cos2 ωt) ∼ − 21 mω 2 cos 2ωt , (1.8)

2
which is a fast variation. Let us see, however, how much I(t) changes over one period
Z t+T Z t+T
dI 0 ω̇ 0 �
(t ) V (t0 ) − K(t0 ) dt0


I(t + T ) − I(t) = dt = (1.9)
t dt0 t ω 2

Since ω(t) is slowly varying, it changes very little over a period T and we can take the factor ω̇/ω out
of the integral: Z t+T
ω̇
I(t + T ) − I(t) ' 2 (t) (V (t) − K(t)) dt0 (1.10)
ω t
In harmonic motion with ω constant, the average over a period of the potential energy V (t) is exactly
equal to the average of the kinetic energy K(t), and the two terms above would cancel exactly. When
ω is slowly changing they roughly cancel

ω̇(t)
I(t + T ) − I(t) ' ·0'0 (1.11)
ω2

What is the geometrical interpretation of the adiabatic invariant E/ω? For this we consider the
motion of a classical oscillator in phase space (x, p) where periodic oscillations trace the ellipse defined
by energy conservation:
p2 1
+ mω 2 x2 = E (ω, E, constants)
2m 2

We quickly see that the semi-major and semi-minor axes have lengths

√
r
2E
a= 2
and b = 2mE (1.12)
mω
Therefore
E
Area of the ellipse = πab = 2π (1.13)
ω
The adiabatic invariant is proportional to the area of the ellipse. That’s neat! We can rewrite the
area as an integral that takes a familiar form:
I
Area of the ellipse = p dx

3
where we integrate over the whole closed trajectory with the orientation shown in the picture so that
the area above the x axis is obtained as we go from left to right and the area under the x axis is
obtained as we go from right to left. In this example
I
p dx = 2πI . (1.14)

More generally, for other systems the left-hand side is an adiabatic invariant. The value of the invariant
is different for different systems, for the oscillator it is 2πE/ω .

1.2 Quantum mechanics systems

What does it suggest for quantum mechanics?
First, for the harmonic oscillator
~ω n + 12
�

E
= ~ n + 12
�

= (1.15)
ω ω
Fixed Eω is fixed quantum number! This suggests that in QM the quantum number doesn’t tend to
change under adiabatic changes. Indeed, we get the same intuition from WKB: consider a potential
with two turning points a, b. We have the Bohr-Sommerfield quantization condition

Z b
1
p(x)dx = n + 12 π
�

~ a

I
p(x)dx = 2π~ n + 12
�

rewritten as (1.16)

The left hand side, as noted before is an adiabatic invariant, so in the semiclassical approximation for
arbitrary potential we find that the quantum number may not change under adiabatic changes! We
will see that indeed that is the case.

The formula for transitions at first order in perturbation theory gives complementary intuition:
2
Z t 0
iωf i t δHf i (t )
f
0
Pf ←i (t) = e dt (1.17)
0 i~

For constant perturbations, δH

f f i is time-independent and

f f i |2 Z t 2 f f i |2 eiωf i T − 1 2
|δH iωf i t 0 |δH
Pf ←i (t) = e dt = . (1.18)
~2 0 ~2 ωf2i
1
• If the spectrum is discrete, it is hard to jump a big energy gap because of the ωf2i
suppression.

1
• For slowly varying perturbations (compared to ωf i ) the ωf2i
suppression will remain.

So it is difficult in general to change state with constant or slow perturbations, suggesting again that
quantum numbers are adiabatic invariants. That is why transitions to the continuum with constant
perturbations essentially conserve energy. And why you need oscillatory perturbations for efficient
transitions between energy levels.

4
2 Adiabatic Evolution
Suppose you have found a ψ(t) such that

H(t)|ψ(t)i = E(t)|ψ(t)i (2.1)

we’ll call |ψ(t)i, defined by (2.1), an instantaneous eigenstate. I’d like to emphasize from the
start that, in general, an instantaneous eigenstate is not a solution of the time dependent Schrödinger
equation. As it turns out, it is a useful tool to construct approximate solutions to the Schrödinger
equation.
Let us try to understand the relation between |ψ(t)i and |Ψ(t)i, the solution to the Schrödinger
equation
i~∂t |Ψ(t)i = H(t)|Ψ(t)i . (2.2)
Let us try an ansatz, building the solution |Ψ(t)i using the instantaneous eigenstate:
 Z t 
1 0 0
|Ψ(t)i = c(t) exp E(t )dt |ψ(t)i , (2.3)
i~ 0

with c(t) a function of time to be determined and where we have included a familiar time dependent
phase. There is no guarantee this ansatz will work but it seems a good try.
The LHS of the Schrödinger equation then looks like
 Z t   Z t 
1 0 0 1 0 0
i~∂t |Ψ(t)i = ċ (t) exp E(t )dt |ψ(t)i + E(t)|Ψ(t)i + c(t) exp E(t )dt |ψ̇(t)i (2.4)
i~ 0 i~ 0

For the RHS, using the instantaneous eigenstate equation, we have

 Z t 
1 0 0
H(t)|Ψ(t)i = c(t) exp E(t )dt H(t)|ψ(t)i = E(t)|Ψ(t)i . (2.5)
i~ 0

Equating the two sides, we get

 Z t   Z t 
1 0 0 1 0 0
ċ(t) exp E(t )dt |ψ(t)i + c(t) exp E(t )dt |ψ̇(t)i = 0
i~ 0 i~ 0

and canceling the two exponentials we have

ċ(t) |ψ(t)i = −c(t) |ψ̇(t)i . (2.6)

Multiply by hψ(t)| we get a differential equation for c(t):

ċ(t) = −c(t) hψ(t)|ψ̇(t)i , (2.7)

which happily we can solve. Letting c(t = 0) = 1 we can write

 Z t 
0 0 0
c(t) = exp − hψ(t )|ψ̇(t )idt . (2.8)
0

5
The above exponential is a phase because the bracket in the integrand is actually purely imaginary:
dψ ∗
Z Z Z
∗ dψ d ∗
hψ(t)|ψ̇(t)i = dx ψ = dx (ψ ψ) − dx ψ
dt dt dt
Z (2.9)
d ∗
= dx ψ ψ − hψ̇(t)|ψ(t)i
dt
Since the wavefunction is normalized we have

hψ(t)|ψ̇(t)i = − hψ̇(t)|ψ(t)i = −hψ(t)|ψ̇(t)i∗ (2.10)

showing that indeed hψ(t)|ψ̇(t)i is purely imaginary. To emphasize this fact we write
 Z t 
0 0 0
c(t) = exp i ihψ(t )|ψ̇(t )idt (2.11)
0

Having apparently solved for c(t) we now return to our ansatz (2.3), we get
 Z t   Z t 
0 0 0 1 0 0
|Ψ(t)i ' c(0) exp i ihψ(t )|ψ̇(t )idt exp E(t )dt |ψ(t)i . (2.12)
0 i~ 0

But there is a mistake in this analysis. We really did not solve the Schrödinger equation! That’s why
we put a ' instead of an equality.
The equation we had to solve, (2.6), is a vector equation, and forming the inner product with hψ(t)|
gives a necessary condition for the solution, but not a sufficient one. We must check the equation form-
ing the overlap with a full basis set of states. Indeed since |ψ(t)i is known, the equation can only have a
solution if the two vectors |ψ̇(t)i and |ψ(t)i are parallel. This does not happen in general. So we really
did not solve equation (2.6). The conclusion is that, ultimately, the ansatz in (2.3) is not good enough!

We can see the complication more formally. At t = 0 equation (2.6) reads

ċ(0)|ψ(0)i = −c(0)|ψ̇(0)i . (2.13)

Using Gram-Schmidt we can construct an orthonormal basis B for the state space with the choice
|ψ(0)i for the first basis vector:
n o
B = |1i = |ψ(0)i, |2i, |3i , . . . . (2.14)

Equation (2.13) requires

hn|ψ̇(0)i = 0 n = 2, 3, . . . (2.15)
This will not hold in general. The key insight, however, is that (2.12) is a fairly accurate solution if
the Hamiltonian is slowly varying. Making the definitions:
1 t
Z Z t
0 0
θ(t) ≡ − E(t )dt , ν(t) ≡ ihψ(t)|ψ̇(t)i , γ(t) ≡ ν(t0 )dt0 (2.16)
~ 0 0

so that θ, ν and γ are all real, the state reads

|Ψ(t)i ' c(0) exp (iγ(t)) exp(iθ(t))|ψ(t)i . (2.17)

6
The phase θ(t) is called the dynamical phase and the phase γ(t) is called the geometric phase.

Comment: Instantaneous eigenstates are rather ambiguous. If one has the |ψ(t)i, they can be modified
by the multiplication by an arbitrary phase:

|ψ(t)i → |ψ 0 (t)i = e−iχ(t) |ψ(t)i . (2.18)

3 Systematic approach
Must use a basis to see the error terms and get a more general picture. We will do this now sys-
tematically. But first let us state precisely the idea in adiabatic approximation. Consider a family of
instantaneous eigenstates:
H(t)|ψn (t)i = En (t)|ψn (t)i (3.1)
with E1 (t) < E2 (t) < . . . , so that there are no degeneracies.
Adiabatic approximation: If at t = 0 |Ψ(0)i = |ψn (0)i for some n, then if H(t) is slowly varying for
0 ≤ t ≤ T then at time T we have |ψ(T )i ' |ψn (T )i up to a calculable phase.
Key facts:

1. The probability to jump to another state |ψk (t)i with k 6= n is highly suppressed.

2. The phases can sometimes be relevant and have geometric meaning. An overall phase cannot be
observed but if we have a superposition

|Ψ(0)i = c1 |ψ1 (0)i + c2 |ψ2 (0)i + . . . (3.2)

the relative phases acquired by |ψ1 (0)i and |ψ2 (0)i after time evolution can matter.

Calculation: X
|Ψ(t)i = cn (t)|ψn (t)i (3.3)
n
Schrödinger equation :
X  X
i~ c˙n |ψn (t)i + cn |ψn˙(t)i = cn (t)En (t)|ψn (t)i (3.4)
n n

act with hψk (t)| from the left:

X
i~c˙k = Ek ck − i~ hψk |ψ˙n icn
n
  X
i~c˙k = Ek − i~hψk |ψ˙k ick − i~ hψk |ψ˙n icn (3.5)
n6=k

We can relate hψk |ψ˙n i to a matrix element of H(t) in the space of instantaneous eigenvectors

H(t)|ψn i = En (t)|ψn i (3.6)

take time derivative

H ˙(t)|ψn i + H(t)|ψ˙n i = E˙n (t)|ψn i + En (t)|ψ˙n i (3.7)

7
multiplty by hψk (t)| with k 6= n

hψk (t)|H ˙(t)|ψn i + Ek (t)hψk (t)|ψ˙n i = E˙n (t)hψk (t)|ψ˙n i (3.8)

hence
hψk (t)|H ˙(t)|ψn i H˙ kn
hψk (t)|ψ˙n i = ≡ (3.9)
En (t) − Ek (t) En − Ek
We can use plug (3.9) back in Eq.(3.5) to get

  X Ḣkn
i~c˙k = Ek − i~hψk |ψ˙k ick − i~ cn (3.10)
En − Ek
n6=k

H˙ kn
Note that if the term proportional to En −Ek vanishes, then |ck | = 1, hence if you start in |ψk i you
stay in |ψk i.
If we ignore the extra term:

1 t
 Z  
ck (t) = ck (0) exp Ek (t0 ) − i~hψk |ψ˙k i dt0
i~ 0
 Z t   Z t 
1 0 0 ˙ 0
= ck (0) exp Ek (t )dt exp i ihψk |ψk idt
i~ 0 0
= ck (0)eiθk (t) eiγk (t) (3.11)

where
Z t
1
θk (t) = − Ek (t0 )dt0 (3.12)
~ 0
νk (t) = ihψk (t)|ψ˙k (t)i (3.13)
Z t
γ(t)k = νk (t0 )dt0 (3.14)
0

8
4 Landau-Zener transitions
Take ψ1 (x; R) and ψ2 (x; R) to be the electronic configurations of a molecule with fixed nuclei separated
at a distance R.
We have

H(R)ψi (x; R) = Ei (R)ψi (x; R) (4.1)

Depending on R the states are polar or non po-

lar changing characteristic near R = R0 . If R
changes slowly, ψ1 remains ψ1 or ψ2 will remain
ψ2 . But if R varies quickly, then ψ1 → ψ2 near
R0 . This would be a non-adiabatic transition.
Thinking of R as a function of time, we have a
time dependent hamiltonian
�

H R(t)

with instantaneous energy eigenstates

�
�

ψi x; R(t) , Ei R(t)

we can now plot the energies for constant velocity R˙

We can sometimes think of this as a 2-level problem; if no other eigenstates are relevant.
So consider a slightly idealized 2 × 2 system
 αt   
2 0 1
H(t) = αt , α>0 |1i = (spin up)
0 −2 0
 
αt αt 0
E1 (t) = , E2 (t) = − |2i = (spin down) (4.2)
2 2 1

9
The instantaneous eigenstates |1i, |2i are actually time independent. Take
   
1 0
|ψ1 i = |ψ2 i = (4.3)
0 1

then
1 t iαt2
 Z   
0 0
|ψ1 (t)i = exp E1 (t )dt |1i = exp − |1i solves the Schrödinger equation (4.4)
i~ 0 4~
 Z t
iαt2
  
1 0 0
|ψ2 (t)i = exp E2 (t )dt |2i = exp + |2i solves the Schrödinger equation (4.5)
i~ 0 4~
 
1
Time evolution is clear: if |ψi = at t = −∞ it will remain in that state forever. Same for
0
 
0
|ψi = .
1
Now make the problem more interesting by perturbing the hamiltonian
 αt 
2 H12
H(t) = ∗ (4.6)
H12 − αt
2

with H12 constant.

At t = 0 the energy eigenvalues are ±|H12 |

10
 αt
H= σz + <(H12 )σx − =(H12 )σy (4.7)
2 r
α 2 t2
E± (t) = ± |H12 |2 + (4.8)
4
we can write H in a compact form by defining the vector
 
αt
a = H12 , 0, = |a|n = E+ (t)n (4.9)
2

taking H12 to be real

so that
H =a·σ (4.10)
The instantaneous energy eigenstates are

±n(t) with energies E± (t)

The instantaneous energy eigenstates change type

   
0 1
→ (polar - non polar)
1 0
   
1 0
→ (non polar - polar)
0 1

|H12 |
An adiabatic process will keep you there. Consider τd for the duration of the change |α| ≡ τα , since

αt |α|t
E1 = → |H12 | = (see fig) (4.11)
2 2
|H12 |
Also ~ ≡ ω12 and it is called Rabi frequency. It’s relevant for the transitions at t = 0 since

0 H12
H(0) = .
H12 0
Process is adiabatic when
|H12 |2
ω12 τα  1 =⇒ 1 (4.12)
~|α|

11
i.e.
2π
= T12  τα (4.13)
ω12
hence, the adiabatic change is much slower than the natural time scale of the system.
Alternatively: The Hamiltonian should not vary much over the time scale T associated with the relevant
energy difference ΔE
dH
T H (4.14)
dt
Approximate T = H~ if ΔE ' H
   
~ dH d 1 ~
 1 =⇒ ~  1 or ∂t (4.15)
H 2 dt dt H E
 
analog of ∂x ~p  1 in WKB.
For our case
d ~ ?
q 1 (4.16)
dt |H |2 + α2 t2
12 4
Let’s check!

d ~ ~α2 t αt
q =  3/2 = ~α 
dt |H |2 + 2 2 3/2

α2 t2 2 2
12 4 |H12 |2 + α 4t |H12 |2 + α 4t

αt ~α|H12 | ~α
≤ max ~α  3/2 ≈ |H |3 = |H |2  1 X
t α2 t2 12 12
|H12 |2 + 4
x
(4.17) Max of (a2 +x2 )3/2
2

Probability for a non-adiabatic transition happens for x2 = a2

|H12 |2
 
Pn.ad. = exp (−2πω12 τα ) = exp −2π (4.18)
~|α|

5 Berry’s phase
Adiabatic theorem: |ψ(t = 0)i = |ψn (0)i and with instantaneous eigenstates
|ψn (t)i we find
|ψ(t)i ' eiθn (t) eiγn (t) |ψn (t)i (5.1)
with, as in (3.12)
Z t
1
θn (t) = − En (t0 )dt0 (5.2)
~ 0
νn (t) = ihψn (t)|ψ˙n (t)i (5.3)
Z t
γn (t) = νn (t0 )dt0 (5.4)
0
We now understand the relevance of γn (t), the geometrical phase:

12
 Assume H depends on a set of coordinates

R(t) = (R1 (t), R2 (t), . . . , RN (t)) (5.5)

several parameters that are tune dependent.

Instantaneous states

H(R)|ψn (R)i = E(R)|ψn (R)i (5.6)

Evaluate the geometric phase. Start by computing

d
νn (t) = i ψn (R(t)) ψn (R(t)) (5.7)
dt
d
we need dt ψn (R(t))

N
d X d dRi ~ R ψn (R(t)) · dR(t)
ψn (R(t)) = ψn (R(t)) =r (5.8)
dt dRi dt dt
i=1

so that
~ R ψn (R(t)) · dR(t)
νn (t) = i ψn (R(t)) r (5.9)
dt
and Z τ Z τ
γn (τ ) ≡ νn (t)dt = ~ R ψn (R(t)) · dR(t) dt
i ψn (R(t)) r (5.10)
0 0 dt
hence the geometrical phase γn (tf ), also known as Berry phase, is
Z Rf
γn (tf ) = ~ R ψn (R) · dR
i ψn (R) r (5.11)
Ri

The integral depends on the path, but does not depend on time!! Whether you take a nano second or
a year to make transition, the geometric phase is the same!

~ R ψn (R) is an N −component object that lives in the parameter space. It is called the
i ψn (R) r
Berry connection An (R), associated with |ψn (t)i

~ R ψn (R)
An (R) = i ψn (R) r (5.12)

In this way we can rewrite the Berry phase as

Z Rf
γn = An (R) · dR (5.13)
Ri

If we redefine the instantaneous states by an overall phase

fn (R)i = e−iβ(R) ψn (R)

ψn (R) → |ψ (5.14)

13
where β(R) is an arbitrary real function, what happens to An (R)?

A
fn (R) = i ψ ~R ψ
fn (R) r fn (R) =

~ R e−iβ(R) ψn (R)
= i ψn (R) eiβ(R) r
 
~ R β(R) hψn (R)|ψn (R)i + An (R)
= i −ir (5.15)
| {z }
1

A ~ R β(R)
fn (R) = An (R) + r (5.16)
analogous to the vector potential in EM (A ~ 0 + rE ).
~0 → A
What about the Berry phase?
Z Rf Z Rf
fn (Rf ) =
γ fn (R) · dR = γn (Rf ) +
A ~ R β(R) · dR =⇒
r (5.17)
Ri Ri

fn (Rf ) = γn (Rf ) + β(Rf ) − β(Ri )

γ (5.18)
The geometrical phase is completely well defined for closed paths in parameter space.
Comments:

• If the ψn (t) are real, then the Berry phase vanishes:

Z
d
νn = ihψn (t)|ψ˙ n (t)i = i dx ψn∗ (t, x) ψn (t, x)
dt
Z Z
d i d 2
= i dx ψn (t, x) ψn (t, x) = dx ψn (t, x) =
dt 2 dt
Z
i d
= dx |ψn (t, x)|2 = 0 , (5.19)
2 dt
since the wavefunction is normalized. This should not be surprising. In general grounds we
have seen that hψn (t)|ψ̇n (t)i is purely imaginary. But if ψn is real this overlap cannot produce
a complex number, so it can only be zero.

• If there is just one coordinate, i.e. R = R, Berry’s phase vanishes for a loop

I
An (R)dR = 0 (5.20)

In here the integral from Ri to Rf is cancelled by the integral back from Rf to Ri .

• In 3D we can make use of Stoke’s theorem to simplify the calculation of γn [C]

I ZZ   ZZ
γn [C] = An (R) · dR = ~ ~
r × An (R) · dS ≡ Dn · dS~ (5.21)
C S S

where S is the surface with boundary C and we defined the Berry curvature Dn

~ × An (R)
Dn ≡ r (5.22)

14
 If we think of the Berry connection as the vector potential, the Berry curvature is the associated
magnetic field. Note that the curvature is invariant under phase redefinition
 
Dn → D0n = r ~ ×A fn (R) = r~ × An (R) + r ~ β(R)
(5.23)
~ × An (R) + r ~ ~  ~
= r  × r
 β( R) = r × A n (R) = D n .

Example: Berry phase for an electron in a slowly varying magnetic field. Take a magnetic
field with fixed intensity and slowly varying direction B(t) = B~n(t), put an electron inside this
magnetic field, so that we get an interaction described by the hamiltonian

H(t) = −µ · B(t) = µB B~n(t) · ~σ (5.24)

The direction of the B field, ~n(t) swipes a closed loop C on the

surface of an imaginary sphere of radius ρ in a time scale T  µB~B .
�

Think of the instantaneous eigenstates χ± R(t) satisfying
�
�

H(t) χ± R(t) = ±µB B χ± R(t) (5.25)

where
R(t) = (r(t) , θ(t) , φ(t)) (5.26)
|{z}
=ρ (fixed)

We get
ZZ ZZ ZZ
~± = 1 ~ ± · dS
~= 1 1 Ω
D rˆ =⇒ γ± [C] = D ˆ 2 dΩ =
rˆ · rr dΩ = (5.27)
2r2 S S 2r2 2 S 2

6 Molecules and Born-Oppenheimer

Molecules are much harder to treat than atoms. Atoms are hard because even though the potential
created by the nucleus is spherically symmetric, the Coulomb interactions between the electrons breaks
the spherical symmetry. In molecules even ignoring Coulomb repulsion between electrons, the potential
created by nuclei that are spatially separated is not spherically symmetric.
In some approximation one can view a molecule as a system in which nuclei in classical equilibrium
with well localized positions while the electrons move around in the Coulomb potential created by the
nuclei. This approximation is reasonable since typically Mm
' 10−4 where m is the electron mass and
M the nuclear one. In this picture slow nuclear vibrations adiabatically deform the electronic states.

In order to make estimates, consider a molecule of size a, so that

~ ~2
pelectron ∼ and Eelectron ∼ (6.1)
a ma2
The positively charged nuclei repell each other but the electrons in between create an effective attrac-
tion that, at equilibrium, cancels the repulsive forces. There will be nuclear vibrations around the
equilibrium configuration. Consider the nuclear oscillations governed by the nuclear Hamiltonian
P2
HN = + 12 kx2 (6.2)
2M

15
The restoring force is determined by k, and it is due to the electron system, with no reference to the
mass M . Since k has units of energy over length-square, we must have

Energy ~2
k = ∼ . (6.3)
L2 ma4
But k = M ω 2 , with ω the frequency of nuclear oscillations so we have

~2 m ~2 m ~2
r
2 2
Mω ∼ → ω ∼ → ~ω ∼ . (6.4)
ma4 M m2 a4 M ma2
We thus find that the nuclear vibrational energies are
r
m
Evibration ∼ Eelectron . (6.5)
M

There are also rotations and their energy Erot is even smaller, as they involve essentially no distortion
of the molecule
L2 ~2 `(` + 1) m ~ m
Erot = ' 2
∼ =⇒ Erotation ' Eelectron (6.6)
2I Ma M ma2 M

Therefore we have the following hierarchy of energies

r
m m
Eelectron : Evibration : Erotation = 1 : : . (6.7)
M M

6.1 Born-Oppenheimer approximation

Consider a molecule with N nuclei and n electrons. The Hamiltonian takes the form

N n
X P2α X p2i
H= + VN N (R) + + VeN (R, r) + Vee (r) , (6.8)
2Mα 2m
α=1 i=1

where Mα with α = 1, . . . , N are the nuclear masses and

Pα , Rα : nuclei canonical variables VN N : nuclei-nuclei interaction

pi , ri : electron canonical variables Vee : electron-electron interaction
R ≡ (R1 , . . . , RN ) VeN : electron-nuclei interaction
r ≡ (r1 , . . . , rn )

The wavefunction ψ(R, r) for the molecule is, in position space, a function of all the nuclear positions
and all the electron positions.
In the limit when Mα /m → ∞ the nuclear skeleton may be considered fixed, making the positions
R are fixed. The electrons then move under the effect of the nuclear potential VeN (R, r) with fixed R,
and the electron-electron Coulomb repulsion. The relevant Hamiltonian He for the electrons is then
n
X p2i
He (p, r; R) = + VeN (R, r) + Vee (r) . (6.9)
2m
i=1

16
This is a different Hamiltonian each time we change the positions R of the nuclei. The associated
Schrödinger equation for the electrons is
n
" #
~2 X 2 (i) (i)
− rri + VeN (R, r) + Vee (r) φR (r) = Ee(i) (R)φR (r) . (6.10)
2m
i=1

The wavefunction for the electrons, as expected, is a function of the position of the electrons r, which
appears as the argument of the wavefunction. Since the wavefunction depends on the nuclear positions,
this dependence is included as a subscript. Finally, the superscript i labels the various wavefunctions
(i)
that may appear as solutions of this equation. The associated energies Ee (R) depend on the nuclear
(i)
positions and the label i. If we calculated all the φR (r) we would have a full basis of electronic
configurations and we could write an ansatz for the full wavefunction of the molecule:
(i)
X
ψ(R, r) = η (i) (R)φR (r) , (6.11)
i

where the η (i) are the unknowns. Substitution into the full Schrödinger equation

Hψ(R, r) = Eψ(R, r) , (6.12)

gives an infinite set of coupled differential equations for η (i) (R). This is too difficult, so we try to
make do with a single term:
ψ(R, r) = η(R)φR (r) , (6.13)
where we would generally use for φR (r) the ground state wavefunction for the electrons in the frozen
nuclear potential. If we have this wavefunction for all R, as we now assume, we also know the value
Ee (R) of the associated energy.

We will do a variational analysis. For this we will compute the expectation value hψ|H|ψi using
ψ(R, r) = η(R)φR (r). We will then utilize the known φR (r) to integrate the electronic dependence in
the expectation value
Z Z
hHi = dRdr ψ ∗ (R, r)H ψ(R, r) = dRdr η ∗ (R)φ∗R (r)H η(R)φR (r)
Z (6.14)
∗
= dR η (R)Heff η(R) ,

thus discovering the effective Hamiltonian Heff for the nuclear degrees of freedom. We begin the
calculation by rewriting the original Hamiltonian:
N
X P2α
H = ĤN + Ĥe , ĤN = + VN N (R) . (6.15)
2Mα
α=1

17
 ˆ e:
As a warmup we calculate the expectation value of H
Z
hHe i = dR dr η ∗ (R)φ∗R (r)Ĥe η(R)φR (r)
Z Z 
∗ ∗
= dR η (R) dr φR (r)Ĥe φR (r) η(R)
| {z }
Ee (R)
Z
= dR η ∗ (R)Ee (R)η(R) . (6.16)

This term has contributed to the effective nuclear Hamiltonian the value of the R dependent electron
energy. Now the nuclear term
 2  Z
Pα 1
= dR dr η ∗ (R)φ∗R (r)Pα Pα (η(R)φR (r))
2Mα 2Mα
Z
1 h�
i
dR dr η ∗ (R)φ∗R (r)Pα Pα η(R) φR (r) + η(R) Pα φR (r)

�
= (6.17)
2Mα

We want to move φ∗R (r) closer to the other φR (r) to be able to do the integrals. For that we use

φ∗R (r)Pα = Pα φR
∗
(r) − Pα φ∗R (r) ,
�

(6.18)

where in the last term, as indicated by the parenthesis, the derivation is acting only on the field φ∗R (r).
Hence
 2  Z
Pα 1 n h
i
dR dr η ∗ (R) Pα φ∗R (r) Pα η(R) φR (r) + φ∗R (r)η(R) Pα φR (r)
�
�
=
2Mα 2Mα

h�
io
− Pα φ∗R (r) Pα η(R) φR (r) + η(R) Pα φR (r)
�
�
(6.19)

We can now move in the dr integral

 2  Z  h Z Z
Pα 1 i
= dR η ∗ (R) Pα Pα η(R) dr φ∗R (r)φR (r) + η(R) dr φ∗R (r)Pα φR (r)
2Mα 2M
Z Z 
∗ ∗
�
�
�
�

− Pα η(R) dr Pα φR (r) φR (r) + η(R) dr Pα φR (r) Pα φR (r) (6.20)

It is now convenient to define

Z Z
Aα (R) ≡ i~ dr φ∗R (r)rRα φR (r) =− dr φ∗R (r)Pα φR (r) (6.21)

This is a Berry connection! We have a full Berry connection for each nucleus (thus the label α). The
Berry connection arises from the electronic configuration. With this definition we have
 2  Z  Z 
Pα 1 ∗ 2
�
2 2
= dR η (R) Pα η(R) − Pα η(R)Aα (R) − Aα (R) Pα η(R) + ~ η(R) dr rRα φR (r)
2Mα 2M
(Pα − Aα )2 A2α ~2
Z  Z 
∗ 2
= dR η (R) − + dr rRα φR η(R) (6.22)
2Mα 2Mα 2Mα

18
Hence
* + Z " #
X P2 X (Pα − Aα )2 X A2 X ~2 Z 2
α
= dR η ∗ (R) − α
+ dr rRα φR η(R) (6.23)
α
2M α α
2M α α
2M α α
2M α

so that the total expression reads

* +
X P2
α
hHi = + VN N (R) + He =
α
2Mα
" #
Z X (Pα − Aα )2 X A2 X ~2 Z 2
= dR η ∗ (R) + VN N (R) + Ee (R) − α
+ dr rRα φR η(R)
α
2M α α
2M α α
2Mα
(6.24)

and separating hHi in kinematics and potential term

" #
Z X (Pα − Aα )2
∗
hHi = dR η (R) + U (R) η(R) (6.25)
α
2Mα

we can read from (6.24) the effective potential U (R)

X ~2 Z 2
X A2 (R)
α
U (R) ≡ VN N (R) + Ee (R) + dr rRα φR − (6.26)
α
2M α α
2Mα

Since  
~ ~ i
Pα − Aα = rRα − Aα = rRα − Aα , (6.27)
i i ~
the Schrödinger equation for nuclear motion is
" 2 #
X ~2  i
− rRα − Aα + U (R) η(R) = Eη(R) (6.28)
α
2M α ~
R 2
Berry’s phases are not there if φR (r) can be chosen to be real (note that we still have the dr rRα φR
term ). Lowest order Born-Oppenheimer:
X ~2
H=− r2Rα + VN N (R) + Ee (R) (6.29)
α
2M α

6.2 Following the direct route

H = ĤN + Ĥe = T̂N + V̂N N + Ĥe (6.30)
where
X ~2
T̂N = r2Rα (6.31)
α
2M α

ˆ e φ(i) = Ee (R)(i) φ(i)

H (6.32)
R R

19
and
(i)
X
ψ= η (i) (R)φR (r) . (6.33)
i
Therefore the eigenvalue equation Hψ = Eψ looks like
 
(i) (i)
X X
Hψ = T̂N η (i) (R)φR (r) + η (i) (R) V̂N N + Ĥe φR (r)
i i
X (i)
X X ~2 h � (i) (i)
i
(T̂N + V̂N N + Ee(i) (R))η (i) (R)φR (r) − 2
2 rRα η (i) (R) rRα φR (r) + η (i) (R)rR

�

= φ
α R
(r)
α
2Mα
i i
(i)
X
=E η (i) (R)φR (r) (6.34)
i
R ∗(j)
We now multiply by dr φR (r)
h i X ~2  � Z
∗(j) (i)
Z
∗(j) (i)

Ee(i) (R) (j) (j) (i) (i) 2


T̂N + V̂N N + η = Eη + 2 rRα η dr φR (r)rRα φR (r) + η drφR (r)rRα φR (r)
2Mα
i,α
(6.35)
Suppose there was no sum over ”i”, so that j = i
X ~2  Z 
(i) 1 (i) ∗(j) 2 (i)
2rRα η Aα (R) + η drφR (r)rRα φR (r)
α
2Mα i~
 Z  Z
(i) ∗(j) (i) (i) 1 (i) ∗(j) (i)
= rRα η drφR (r)rRα φR (r) − (rRα η ) Aα (R) − η drrRα φR (r)rRα φR (r) =
i~
  Z
i i 1 (i)1  
(i) (j) 2
= Pα η Aα − (rR α η ) Aα (R) − η dr rRα φR (r) (6.36)
~ i~  i~
Back Z Z
X 1 (j) 2
Pα η i Aα − Aα Pα η (i) −η (i)
�

dr rRα φR (r) (6.37)
α
2Mα
would get perfect agreement!!

6.3 The H2+ ion

The electron Hamiltonian is

~2 2 2
 
1 1
He = − r −e + (6.38)
| 2m
{z } | r1 r2
{z }
T̂e VN e

Do a variational ansatz
1 − r
ψ = A[ψ0 (r1 ) + ψ0 (r2 )] ψ0 (r) = p 3 e a0 (6.39)
πa0
Impose normalization of the wavefunction
"  2 #
1 R R 1 R
|ψ|2 = 1 =⇒ |A|2 = with I≡e a 1+ + (6.40)
2(1 + I) a 3 a

20
Since hHe i ' Ee (R) the full potential is

Ee (R) + VN N (R) (6.41)

| {z }
e2
R

Experimentally we have R = 1.06˚ A and E = −2.8 eV.

Ansatz is not very accurate, for small R wavefunction becomes ground state of Hydrogen atom not
ground state of Helium, as it should.

21
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8.06 Quantum Physics III

Spring 2018

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Chapter 7

Scattering

c B. Zwiebach
In high energy physics experiments a beam of particles hits a target composed of par-
ticles. By detecting the by-products one aims to study the interactions that occur during
the collision.

Collisions can be rather intricate. For example, the particles involved may be not
elementary (protons) or they may be elementary (electrons and positrons)
p+p → p + p + π0
p+p → p + n + π+
e+ + e− → µ + + µ−
The final products may not be the same as the initial particles. Some particles may be
created.
Here collisions are like reactions in which
a+b → c + d + e + ...
We have scattering when the particles in the initial and final state are the same
a+b → a+b

133
134 CHAPTER 7. SCATTERING

The scattering is elastic if none of the particles internal states change in the collision1 . We
will focus on elastic scattering of particles without spin in the nonrelativistic approximation.

We will also assume that the interaction potential is translational invariant, that is,
V (r1 − r2 ). It follows that in the CM frame the problem reduces, as we did for hydrogen
atom, to scattering of a single particle of reduced mass off a potential V (r). We will work
with energy eigenstates and we will not attempt to justify steps using wave-packets.

7.1 The Schrödinger equation for elastic scattering

We are interested in energy eigenstates

p2
H= + V (r) (7.1.1)
2M
iEt
ψ(r, t) = ψ(r)e− ~ (7.1.2)
~2 2
 
− ∇ + V (r) ψ(r) = Eψ(r) (7.1.3)
2M

Figure 7.1: Potential is finite range, or vanishes faster than 1 r as r → ∞

Will be consider solutions with positive energy. The energy is the energy of the particle
2 k2
far away from the potential, E = ~2M . The Schrödinger equation then takes the form

~2
 
2 2


− ∇ + k + V (r) ψ(r) = 0 (7.1.4)
2M

Now we must set up the waves! Recall the 1D case. Physics dictates the existence of
three waves: an incoming one, a reflected one, and a transmitted one. We can think of
the reflected and transmitted waves as the scattered wave, the waves produced given the
incoming wave. Setting up the waves is necessary in order to eventually solve the problem
by looking into the details in the region where the potential is non-zero. When the potential
has finite range the incoming and scattered waves are simple plane waves that are easily
1
Frank-Hertz experiment involved inelastic collisions of electrons with mercury atoms in which the mer-
cury atoms are excited.
7.1. THE SCHRÖDINGER EQUATION FOR ELASTIC SCATTERING 135

written.

Equation (7.1.4) has an inifinite degeneracy of energy eigenstates. When V (r) ≡ 0, for
example, eik·x for any k such that k · k = k 2 is a solution. Assume an incident wave moving
towards +ẑ. Then the wavefunction will look like

ϕ(r) = eikz (7.1.5)

If we assume V (r) has a finite range a, this ϕ(r) satisfies (7.1.4) for any r > a. For r < a,
however, it does not satisfy the equation; ϕ(r) is a solution everywhere only if the potential
vanishes.
Given an incident wave we will also have a scattered wave. Could it be an ψ(r) = eikr
that propagates radially out?

∇2 + k 2 eikr =


6 0 fails badly for r 6= 0!! (7.1.6)

On the other hand

eikr
∇2 + k 2 =0 for r 6= 0 . (7.1.7)
r
This is consistent with the radial equation having a solution u(r) = eirk in the region where
the potential vanishes. Recall that the full radial solution takes the form u(r)/r.
ikr
Can the scattered wave therefore be e r ? Yes, but this is not general enough. We need to
introduce some angular dependence. Hence our ansatz for the scattered wave is
eikr
ψs (r) = fk (θ, φ) ( 7.1.8)
r
We expect the intensity of the scattered wave to depend on direction and the function
fk (θ, φ) does that. We will see that ψs is only a solution for r  a, arbitrarily far.
Both the incident and the scattered wave must be present, hence the wavefunction is

eikr
ψ(r) = ψs (r) + ϕ(r) ' eikz + fk (θ, φ) , r  a. (7.1.9)
r
136 CHAPTER 7. SCATTERING

As indicated this expression is only true far away from the scattering center. We physically
expect fk (θ, φ) to be determined by V (r). fk (θ, φ) is called the scattering amplitude.

We now relate fk (θ, φ) to cross section!!

h i
# particles scattered per unit time
into solid angle dΩ about (θ, φ)
dσ = h i (7.1.10)
flux of incident particles = # particles
area · time

dσ is called differential cross section, it’s the area that removes from the incident beam the
particles to be scattered into the solid angle dΩ. Let us calculate the numerator and the
denominator. First the denominator, which is the probability current:
Incident flux = ~ Im [ψ ∗ ∇ψ] = ~k ẑ (7.1.11)
in eikz m m
Intuitively, this can be calculated by multiplying the probability density |eikz |2 = 1, by the
p
velocity m = ~k
m . The result is again an incident flux equal in magnitude to m .
~k

To calculate the numerator we first find the number of particles in the little volume of
thickness dr and area r2 dΩ

dn = number of particles in this little volume

2
eikr
dn = |ψ(r)|2 d3 r = fk (θ, φ) r2 dΩ dr = |fk (θ, φ)|2 dΩ dr (7.1.12)
r
dr
With velocity v = ~k
m all these particles in the little volume will go cross out in time dt = v ,
therefore the number of particles per unit time reads
dn dΩ dr ~k
= |fk (θ, φ)|2 dr = |fk (θ, φ)|2 dΩ
dt v
m
Back in the formula for the cross section we get
 |fk (θ, φ)|2 dΩ
~k
dσ = m ~k
m


hence
dσ
Differential cross section: = |fk (θ, φ)|2 (7.1.13)
dΩ
Z Z
Total cross section: σ = dσ = |fk (θ, φ)|2 dΩ (7.1.14)
7.2. PHASE SHIFTS 137

7.2 Phase shifts

Assume V (r) = V (r), so that we are dealing with a central potential. First recall the
description of a free particle in spherical coordinates. With

~2 k 2 uE` (r)
V = 0, E= , ψ(r) = Y`m (Ω) (7.2.1)
2m r
the Schrödinger equation for uE`

~2 d2 ~2 `(` + 1) ~2 k 2
 
− + uE` (r) = uE` (r)
2m dr2 2m r2 2m
d2
 
`(` + 1)
− 2+ uE` (r) = k 2 uE` (r) . (7.2.2)
dr r2

Now take ρ = kr, then (7.2.2) reads

d2
 
`(` + 1)
− 2+ uE` (ρ) = uE` (ρ) (7.2.3)
dρ ρ2

Since k2 disappeared from the equation, the energy is not quantized. The solution to (7.2.3)
is
uE` (ρ) = A` ρj` (ρ) + B` ρ n` (ρ) or uE` (r) = A` rj` (kr) + B` r n` (kr) (7.2.4)
where

j` (ρ) is the spherical Bessel function j` (ρ) is non singular at the origin
n` (ρ) is the spherical Neumann function n` (ρ) is singular at the origin

Both have finite limits as ρ → ∞

 
`π
ρ j` (ρ) → sin ρ − (7.2.5)
2
 
`π
ρ n` (ρ) → − cos ρ − (7.2.6)
2

Now, with the plane wave a solution, we must have

∞
X
eikz = eikr cos θ = a` P` (cos θ)j` (kr) (7.2.7)
`=0

for some coefficients a` . Using

r Z 1
2` + 1 1
Y`,0 (θ) = P` (cos θ) and j` (x) = ` eixu P` (u)du (7.2.8)
4π 2i −1
138 CHAPTER 7. SCATTERING

it can be shown that

∞
ikz
√ X √
e = 4π 2` + 1 i` Y`,0 (θ)j` (kr) . (7.2.9)
`=0

This is an incredible relation in which a plane wave is built by a linear superposition of

spherical waves with all possible values of angular momentum! Each ` contribution is a
partial wave. Each partial wave is an exact solution when V = 0.
We can see the spherical ingoing and outgoing waves in each partial wave by expanding
(7.2.9) for large r:
`π `π
" #
1 ei(kr− 2 ) e−i(kr− 2 )
 
1 `π
j` (kr) → sin kr − = − (7.2.10)
kr 2 2ik r r

Thus
√ ∞ `π `π
ikz 4π X √ ` 1 h ei(kr− 2 ) e−i(kr− 2 ) i
e = 2` + 1 i Y`,0 (θ) − , ra (7.2.11)
k 2i | {z r } | {z r
`=0 }
outgoing incoming

7.2.1 Calculating the scattering amplitude in terms of phase shifts

Recall 1D case

1  ikx 
ϕ(x) = sin(kx) = e − e|−ikx solution if V = 0
2i {z }
ingoing

(7.2.12)
Exact solution
1  ikx 2iδk 
ψ(x) = e e − e|−ikx for x > a (7.2.13)
2i {z }
same
ingoing
wave

where the outgoing wave can only differ from the ingoing one by a phase, so that probability
is conserved. Finally we defined

ψ(x) = ψs (x) + ϕ(x) (7.2.14)

So do a similar transformation to write a consistent ansatz for ψ(r). We have from (7.1.9)

eikr
ψ(r) ' eikz + fk (θ) , r  a. (7.2.15)
r
7.2. PHASE SHIFTS 139

The incoming partial waves in the left-hand side must be equal to the incoming partial
waves in eikz since the scattered wave is outgoing. Introducing the phase shifts on the
outgoing waves of the left-hand side we get
√ ∞ `π `π
4π X √ ` 1 h ei(kr− 2 ) e2iδk e−i(kr− 2 ) i eikr
ψ(r) = 2` + 1 i Y`,0 (θ) − = eikz + fk (θ)
k 2i | r r r
`=0 {z } | {z }
outgoing incoming

The incoming partial waves in eikz cancel in between the two sides of the equation, and
moving the outgoing partial waves in eikz into the other side we get
√ ∞  eikr e− i`π
4π X √ ` 1  2iδ` 2 eikr
2` + 1 i Y`,0 (θ) e −1 = fk (θ) (7.2.16)
k |2i r r
`=0 {z }
eiδ` sin δ`
√ ∞
4π X √ eikr
= 2` + 1 Y`,0 (θ)eiδ` sin δ` , (7.2.17)
k r
`=0

i`π
where we noted that e− 2 = (−i)` and i` (−i)` = 1. Therefore we get
√ ∞
4π X √
fk (θ) = 2` + 1 Y`,0 (θ)eiδ` sin δ` . (7.2.18)
k
`=0

This is our desired expression for the scattering amplitude in terms of phase shifts.
We had
dσ = |fk (θ)|2 dΩ (7.2.19)
and this differential cross section exhibits θ dependence. On the other hand for the full
cross section the angular dependence, which is integrated over, must vanish
Z Z
2
σ = |fk (θ)| dΩ = fk∗ (θ)fk (θ)dΩ
4π X √ √
Z
0 −iδ` iδ`0 ∗
= 2 2` + 1 2` + 1 e sin δ` e sin δ`0 dΩ Y`,0 (Ω)Y`0 ,0 (Ω)
k
`,`0 | {z }
δ``0

Hence
∞
4π X
σ= (2` + 1) sin2 δ` . (7.2.20)
k2
`=0

Now let us explore the form of f (θ) in the forward direction θ = 0. Given that
r r
2` + 1 2` + 1
Y`,0 (θ) = P` (cos θ) =⇒ Y`,0 (θ = 0) =
4π 4π
140 CHAPTER 7. SCATTERING

then √ ∞ r ∞
4π X √ 2` + 1 iδ` 1X
fk (θ = 0) = 2` + 1 e sin δ` = (2` + 1)eiδ` sin δ`
k 4π k
`=0 `=0
Hence
∞
1X 1 k2
Im(f (0)) = (2` + 1)eiδ` sin2 δ` = σ (7.2.21)
k k 4π
`=0

Therefore we have found out a remarkable relation between the total elastic cross section
and the imaginary part of the forward (θ = 0) scattering amplitude. This relation is known
as the Optical theorem and reads

4π
σ= Im(f (0)) . Optical Theorem
k

Let us consider ways in which we can identify the phase shifts δk . Consider a solution,
restricted to a fixed `

ψ(x) = (A` j` (kr) + B` n` (kr)) Y`,0 (θ) x>a (7.2.22)

`

If B 6= 0 then V =
6 0. As a matter of fact, if V = 0 the solution should be valid everywhere
and n` is singular at the origin, thus B` = 0.
Now, let’s expand ψ(x)|` for large kr as in (7.2.10)
    
A` `π B` `π
ψ(x) ' sin kr − − cos kr − Y`,0 (θ) (7.2.23)
` kr 2 kr 2
Define
B`
tan δ` ≡ − ( 7.2.24)
A`
We must now confirm that this agrees with the postulated definition as a relative phase
between outgoing and ingoing spherical waves. We thus calculate
    
1 `π sin δ` `π
ψ(x) ' sin kr − + cos kr − Y`,0 (θ)
` kr 2 cos δ` 2
 
1 `π
' sin kr − + δ` Y`,0 (θ) (7.2.25)
kr 2

1 1 h i(kr− `π +δ` ) `π
i
= e 2 − e−i(kr− 2 +δ` ) Y`,0 (θ)
kr 2i
1 1 h i(kr− `π +2δ` ) `π
i
' e−iδ e 2 − e−i(kr− 2 ) Y`,0 (θ) (7.2.26)
kr 2i
7.2. PHASE SHIFTS 141

This shows that our definition of δk above is indeed consistent the expansion in (7.2.16).
Finally we can read the phase shift from (7.2.25)
 
1 `π
ψ(x) ' sin kr − + δ` Y`,0 (θ) ra (7.2.27)
` kr 2
in the partial wave solution.
As an aside note that both the outgoing and ingoing components of a partial wave are
separately acceptable asymptotic solutions obtained as:
• If A` = −iB`
`π
ei(kr− 2 )
    
`π `π Y`,0 (θ)
ψ(x) ∼ i sin kr − + cos kr − ∼ Y`,0(θ) (7.2.28)
` 2 2 kr kr

• If A` = iB`
`π
e−i(kr− 2 )
ψ(x) ∼ Y`,0 (θ) (7.2.29)
` kr
Each wave is a solution, but not a scattering one.

7.2.2 Example: hard sphere

(
∞ r≤a
V (r) = (7.2.30)
0 r>a

Radial solution
u
R` (r) = = A` j` (kr) + B` n` (kr) (7.2.31)
r
X
ψ(a, θ) = R` (a)P` (cos θ) ≡ 0 (7.2.32)
`
The P` (cos θ) are complete, meaning that

0 = R` (a) = A` j` (ka) + B` n` (ka) ∀ ` (7.2.33)

Recalling
B` j` (ka)
tan δ` ≡ − = (7.2.34)
A` n` (ka)
this implies all phase shifts are determined

j` (ka)
tan δ` = (7.2.35)
n` (ka)
142 CHAPTER 7. SCATTERING

We can now easily compute the cross section σ, which, recalling (7.2.20) is proportional to
sin2 δ`
tan2 δ` j`2 (ka)
sin2 δ` = 2 = 2 (7.2.36)
1 + tan δ` j` (ka) + n2` (ka)
hence
∞ ∞
4π X 2 4π X j`2 (ka)
σ= 2 (2` + 1) sin δ` = 2 (2` + 1) 2 (7.2.37)
k k j` (ka) + n2` (ka)
`=0 `=0

Griffiths gives you the low energy ka  1 expansion

∞  ` 4
4π X 1 2 `!
σ' 2 (ka)4`+2 (7.2.38)
k 2` + 1 (2`)!
`=0

At low energy the dominant contribution is from ` = 0

4π
σ' (ka)2 = 4πa2 Full area of the sphere!
Not the cross section!
(7.2.39)
k2
One more calculation!
eiδ − e−iδ e2iδ − 1 1 + i tan δ
i tan δ = = =⇒ e2iδ = (7.2.40)
eiδ + eiδ e2iδ + 1 1 − i tan δ
Therefore
1 + i nj``(ka)
(ka) n + ij i(j − in)
e2iδ` = = = (7.2.41)
1− i nj``(ka)
(ka)
n − ij −i(j + in)

j` (ka) − in` (ka) Hard sphere

e2iδ` = , phase shifts (7.2.42)
j` (ka) + in` (ka)

7.2.3 General computation of the phase shift

Suppose you have a radial solution R` (r) known for r ≤ a (V (r ≥ a) = 0). This must be
matched to the general solution that holds for V = 0, as it holds for r > a:

At r = a must match the function and its derivative

R` (a) = A` j` (ka) + B` n` (ka) (7.2.43)

7.2. PHASE SHIFTS 143
 
aR`0 (a) = ka A` j`0 (ka) + B` n0` (ka) (7.2.44)
Let’s form the ratio and define β` as the logarithmic derivative of the radial solution

aR`0 (a) A` j` (ka) + B` η`0 (ka) j` (ka) + B ` 0

A` η` (ka) j` (ka) − tan δ` η`0 (ka)
β` ≡ = ka = ka = ka
R` (a) A` j` (ka) + B` n` (ka) j` (ka) + B
A` n` (ka)
` j` (ka) − tan δ` n` (ka)
(7.2.45)
In principle we can use eq. (7.2.45) to get tan δ`, but let’s push the calculation further to
extract the phase shift from e2iδ`

j` cos δ` − η`0 sin δ` j` eiδ` + e−iδ` + iη`0 eiδ` − e−iδ`

β` = ka = ka
j` cos δ` − n` sin δ` j` (eiδ` + e−iδ` ) + in` (eiδ` − e−iδ` )

eiδ` (j` + iη`0 ) + e−iδ` (j` − iη`0 ) e2iδ` (j` + iη`0 ) + (j` − iη`0 )
= ka = ka (7.2.46)
eiδ` (j` + in` ) + e−iδ` (j` − in` ) e2iδ` (j` + in` ) + (j` − in` )

Solve for e2iδ`

ka(j` − iη`0 ) − β` (j` − in` )
e2iδ` = − (7.2.47)
ka(j` + iη`0 ) − β` (j` + in` )
which can be rewritten as

 β − ka j` −iη`0
  

j` − in`  ` j −in
e2iδ` = −  ` 0`   (7.2.48)
j` + in` j +iη
β` − ka j``+in``

which we can also write as

j` −iη`0
  
β` − ka j` −in`
e2iδ` = 2iξ`
e|{z}  
j` +iη`0
 (7.2.49)
Hard sphere β` − ka j` +in`
phase shift

Phase shifts are useful when a few of them dominate the cross section. This happens
when ka < 1 with a the range of the potential. So short range and/or low energy.
1. Angular momentum of the incident particle is L = b · p with b impact parameter and
p momentum

`
L ' bp → ~` ' b~k → b' (7.2.50)
k
144 CHAPTER 7. SCATTERING

When b > a there is no scattering

`
>a Expect no scattering for ` > ka (7.2.51)
k
Thus only values ` ≤ ka contribute to σ.

2. Confirm the impact parameter intuition from partial wave expression. Consider the
free partial wave ∼ j` (kr)Y`,0 . The impact parameter b` of such a wave would be
estimated to be `/k.
Recall that j` (kr) is a solution of the V = 0 radial equation with angular momentum
` and energy ~2 k 2 /(2m). Setting the effective potential equal to the energy:

~2 `(` + 1) ~2 k 2
= (7.2.52)
2mr2 2m
we find that the turning point for the solution is at

k 2 r2 = `(` + 1) . (7.2.53)

Thus we expect j` (kr) to be exponentially small beyond the turning point

p
kr ≤ `(` + 1) ' ` (7.2.54)

confirming that the wave is negligible for r less than the impact parameter `/k!

Figure 7.2: Plot of ρ2J 2 ` (ρ)

7.3 Integral scattering equation

Some useful approximations can be made when we reformulate the time-independent Schrödinger
equation as an integral equation. These approximations, as opposed to the partial waves
method, allow us to deal with potentials that are not spherically symmetric. We consider
the Schrödinger equation

~2 2
 
− ∇ + V (r) ψ(r) = Eψ(r) , (7.3.1)
2M
7.3. INTEGRAL SCATTERING EQUATION 145

set the energy equal to that of a plane wave of wavenumber k and rewrite the potential in
terms of a rescaled version U (r) that simplifies the units:

~2 k 2 ~2
E= and V (r) = U (r) (7.3.2)
2M 2M
then the Schrödinger equation reads

−∇2 + U (r) ψ(r) = k 2 ψ(r)

 
(7.3.3)

rewrite as
∇2 + k 2 ψ(r) = U (r)ψ(r)


(7.3.4)
This is the equation we want to solve.
Let us introduce G(r − r0 ), a Green function for the operator ∇2 + k 2 , i.e.

∇2 + k 2 G(r − r0 ) = δ (3) (r − r0 )


(7.3.5)

Then we claim that any solution of the integral equation

Z
ψ(r) = ψ0 (r) + d3 r0 G(r − r0 )U (r0 )ψ(r0 ) (7.3.6)

where ψ0 (r) is a solution of the homogeneus equation

∇2 + k 2 ψ0 (r) = 0


(7.3.7)

is a solution of equation (7.3.4). Let’s check that this is true

Z
2 2 2 2
d3 r0 G(r − r0 )U (r0 )ψ(r0 )



∇r + k ψ(r) = ∇r + k
Z
= d3 r0 δ (3) (r − r0 )U (r0 )ψ(r0 )

= U (r)ψ(r) X (7.3.8)

To find G we first recall that

 ±ikr
e±ikr
 Ce 6 0
for r = as a matter of fact ∇2r + k 2 = 0 ∀ r 6= 0
r r
G(r) ∼
− 1 for r → 0 as a matter of fact 1
∇2 − 4πr


= δ 3 (r)
4πr
(7.3.9)

Thus try
1 e±ikr
G± (r) = − (7.3.10)
4π r
146 CHAPTER 7. SCATTERING

and we are going to refer to G+ as the outgoing wave Green function and to G− as the
ingoing wave Green function.
Let’s verify that this works, write G as a product: G± (r) = e±ikr − 4πr 1


, so that
     
2

2 ±ikr
 1 ±ikr 2 1 
~ ±ikr

~ 1
∇ G± (r) = ∇ e − + e ∇ − + 2 ∇e ·∇ −
4πr 4πr 4πr
(7.3.11)
Recall that
r
∇2 = ∇ · ∇ , ∇r = , ∇ · (f A) = ∇f · A + f ∇ · A (7.3.12)
r
Therefore  
±ikr r ±ikr 2 ±ikr 2ik
∇e = ±ik e , ∇ e = −k ± 2
e±ikr (7.3.13)
r r
then
   
2ik ±ikr 1  r  r 
2
∇ G± (r) = −k ± 2
e − + e±ikr δ 3 (r) + 2 ±ike±ikr ·
r 4πr r 4πr3
2ik ±ikr
 2ik ±ikr

= −k 2 G± (r) ∓ e + δ 3 (r) ± e
 4πr  4πr
= −k 2 G± (r) + δ 3 (r) X (7.3.14)
We will use
ψ0 (r) = eikz and G = G+ (7.3.15)
Thus, with these choices, (7.3.6) takes the form
Z
ψ(r) = eikz + d3 r0 G+ (r − r0 )U (r0 )ψ(r0 ) (7.3.16)

where 0
1 eik|r−r |
G+ (r − r0 ) = − (7.3.17)
4π |r − r0 |
We now want to show that this is consistent with our asymptotic expansion for the energy
eigenstates. For that we can make the following approximations
For the G+ denominator: |r − r0 | ' r (7.3.18)
0 0
For the G+ numerator: |r − r | ' r − n · r (7.3.19)
where

r
n≡
r
7.3. INTEGRAL SCATTERING EQUATION 147

In this way
1 ikr −ikn·r0
G+ (r − r0 ) = − e e (7.3.20)
4πr
Thus  Z  ikr
ikz 1 3 0 −ikn·r0 0 0 e
ψ(r) = e + − d re U (r )ψ(r ) (7.3.21)
4π r
The object in brackets is a function of the unit vector n in the direction of r. This shows that
the integral equation, through the choice of G, incorporates both the Schrödinger equation
and the asymptotic conditions. By definition, the object in brackets is fk (θ, φ), i.e.
Z
1 0
fk (θ, φ) = − d3 r0 e−ikn·r U (r0 )ψ(r0 ) . (7.3.22)
4π
Of course, this does not yet determine fk as the undetermined wavefunction ψ(r) still
appears under the integral. The incident wave has the form of eiki ·r with ki the incident
wave number, |ki | = k. For the outgoing wave we define ks ≡ nk (in the direction of n),
the scattered wave vector. The expression for ψ(r) then becomes
 Z  ikr
iki ·r 1 3 0 −iks ·r0 0 0 e
ψ(r) = e + − d re U (r )ψ(r ) (7.3.23)
4π r
We will do better with the Born approximation.

7.3.1 The Born approximation

Consider the original integral expression:
Z
iki ·r
ψ(r) = e + d3 r0 G+ (r − r0 )U (r0 )ψ(r0 ) (7.3.24)

Rewrite by just relabeling r → r0

Z
0
ψ(r0 ) = eiki ·r + d3 r00 G+ (r0 − r00 )U (r00 )ψ(r00 ) . (7.3.25)

Now plug (7.3.25) under the integral in (7.3.24) to get

Z Z Z
iki ·r 3 0 0 0 iki ·r0
ψ(r) = e + d r G+ (r−r )U (r )e + d r G+ (r−r )U (r ) d3 r00 G+ (r0 −r00 )U (r00 )ψ(r00 )
3 0 0 0

(7.3.26)
Repeat the trick once more to find
Z
0
ψ(r) = eiki ·r + d3 r0 G+ (r − r0 ) U (r0 )eiki ·r
Z Z
00
+ d3 r0 G+ (r − r0 )U (r0 ) d3 r00 G+ (r0 − r00 ) U (r00 )eiki ·r
Z Z Z
+ d3 r0 G+ (r − r0 )U (r0 ) d3 r00 G+ (r0 − r00 )U (r00 ) d3 r000 G+ (r000 − r00 )U (r000 )ψ(r000 )
(7.3.27)
148 CHAPTER 7. SCATTERING

By iterating this procedure we can form an infinite series which schematically looks like
Z Z Z Z Z Z
ψ = eiki ·r + G U eiki r + GU G U eiki r + GU GU G U eikir + . . . (7.3.28)

The approximation in which we keep the first integral in this series and set to zero all others is
called the first Born approximation. The preparatory work was done in (7.3.23), so we
have now
Z  ikr
Born iki ·r 1 3 0 −iks ·r0 0 iki ·r0 e
ψ (r) = e − d re U (r )e (7.3.29)
4π r

hence
Z
1
fkBorn (θ, φ) = − d3 re−iK·r U (r) . (7.3.30)
4π

Here we defined the wave-number transfer K:

|ki | = |ks | , K ≡ ks − ki (7.3.31)

Note that we eliminated the primes on the variable of integration – it is a dummy variable
after all. The wave-number transfer is the momentum that must be added to the incident
one to get the scattered one. We call θ the angle between ki and ks (it is the spherical
angle θ if ki is along the positive z-axis).
Note that
K = |K| = 2k sin 2θ (7.3.32)

In the Born approximation the scattering amplitude fk (θ, φ) is simply the Fourier transform
of U (r) evaluated at the momentum transfer K! fk (θ, φ) captures some information of V (r).
If we have a central potential V (r) = V (r), we can simplify the expression for the Born
scattering amplitude further by performing the radial integration. We have
Z
1 2m
fkBorn (θ) = − d3 re−iK·r V (r) . (7.3.33)
4π ~2

By spherical symmetry this integral just depends on the norm K of the vector K. This is
why we have a result that only depends on θ: while K is a vector that depends on both θ
and φ, its magnitude only depends on θ. To do the integral think of K fixed and let Θ be
7.3. INTEGRAL SCATTERING EQUATION 149

the angle with r

Z ∞ Z 1
m
fk (θ) = − 2πdr r2 d(cos Θ)e−iKr cos Θ V (r)
2π~2 0 −1

∞ ∞
e−iKr − eiKr
Z Z  
m 2 m 2 2 sin(Kr)
=− 2 dr r V (r) =− 2 dr r V (r) (7.3.34)
~ 0 −iKr ~ 0 Kr

hence
Z ∞
2m
fk (θ) = − dr rV (r) sin(Kr) (7.3.35)
K~2 0

with K = 2k sin 2θ .

The Born approximation treats the potential as a perturbation of the free particle waves.
This wave must therefore have kinetic energies larger than the potential. So most naturally,
this is a good high-energy approximation.

Example: Yukawa potential Given

e−µr
V (r) = V (r) = β β, µ > 0 (7.3.36)
r
from (7.3.35), one gets
Z ∞
2mβ 2mβ
fk (θ) = − dr e−µr sin(Kr) = − . (7.3.37)
K~2 0 ~2 (µ2
+ K 2)

We can give a graphical representation of the Born series. Two waves reach the desired
point r. The first is the direct incident wave. The second is a secondary wave originating at
the scattering “material” at a point r0 . The amplitude of a secondary source at r0 is given
by the value of the incident wave times the density U (r0 ) of scattering material at r0 .
In the second figure again an incident wave hits r. The secondary wave now takes
two steps: the incident wave hits scattering material at r00 which then propagates and hits
scattering material at r0 , from which it travels to point r.
150 CHAPTER 7. SCATTERING

Figure 7.3: Pictorial view of Born approximation. Wave at r is the sum of the free incident wave at r,
plus an infinite number of waves coming from the secondary source at r0, induced by the incident
wave.

Figure 7.4: Pictorial view of second order Born term

Figure 7.5: Given (θ, φ) and k (∼ energy), K is determined.

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8.06 Quantum Physics III

Spring 2018

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Chapter 8

Identical Particles

c B. Zwiebach
Two particles are identical if all their intrinsic properties (mass, spin, charge, magnetic
moment, etc.) are the same and therefore no experiment can distinguish them. Of course,
two identical particles can have different momentum, energy, angular momentum. For
example all electrons are identical, all protons, all neutrons, all hydrogen atoms are identical
(the possible excitation states viewed as energy, momentum, etc.)

8.1 Identical particles in Classical Mechanics

We can assign a labeling of the particles and follow through. Results are labeling indepen-
dent.
As shown in Fig.8.2 we have two cases:
• Case 1: Assume we solve the dynamics and find
r1 (t) = r(t) with r(t0 ) = r0
0
r2 (t) = r (t) with r0 (t0 ) = r00

• Case 2: Since the particles are identical the Hamiltonian must make this clear
H(r1 , p1 ; r2 , p2 ) = H(r2 , p2 ; r1 , p1 ) (8.1.1)
This time, when we solve
r1 (t) = r0 (t) with r0 (t0 ) = r00
r2 (t) = r(t) with r(t0 ) = r0

The two descriptions are equivalent. We can follow the particles and the particle that
started at {r0 , p0 } will be at r(t), while the one that started at {r00 , p00 } will be at r0 (t).

In conclusion, we choose one labeling, just as if the particles were different. Follow
through without regard to other possible labeling.

151
152 CHAPTER 8. IDENTICAL PARTICLES

Figure 8.1: Example of two different ways of labeling the initial state

8.2 Identical particles in Quantum Mechanics

8.2.1 Exchange degeneracy
If we cannot follow particles once they overlap and/or collide, we can’t know what alternative
took place.
Question: How to write kets for the initial and final states?

Simpler case to see the complications Let there be two spin-1/2 particles. Consider only
their spin1 , one is |+i, the other |−i. Recall tensor product |vi i(1) ⊗ |vj i(2) describing
particle 1 in state vi and particle 2 in state vj . More briefly |vi i(1) ⊗ |vj i(2) ≡ |vi i ⊗ |vj i
with the understanding that the first ket is for particle 1 and the second for particle 2.
What is the state of the two spin 1/2 particles?

|+i(1) ⊗ |−i(2) or |−i(1) ⊗ |+i(2) (8.2.1)

A priori either one! This, despite the fact that in our conventions for inner products these
two states are orthogonal! Can we declare these states to be physically equivalent and thus
solve the ambiguity? No. If the two states above are equivalent we would have to admit
that even the states
|ψi = α|+i ⊗ |−i + β|−i ⊗ |+i (8.2.2)
1
in this approximation we could say that they are static and very close to each other, even on top of each
other
8.2. IDENTICAL PARTICLES IN QUANTUM MECHANICS 153

Figure 8.2: Example of two different processes involving identical particles. In principle, in
quantum mechanics it is impossible to tell which one happened.

with |α|2 + |β|2 = 1 for normalization, are equivalent. This ambiguity in the specification
of a state of identical particles is called exchange degeneracy.
What is the probability to find these particles in the |+, χi ⊗ |+, χi state?
This states is

1   1  
|ψ0 i = √ |+i(1) + |−i(1) ⊗ √ |+i(2) + |−i(2)
2 2
1 
= |+i(1) ⊗ |+i(2) + |+i(1) ⊗ |−i(2) + |−i(1) ⊗ |+i(2) + |−i(1) ⊗ |−i(2) (8.2.3)
2

the probability is
2 1 2
hψ0 |ψi = (α + β) (8.2.4)
2
thus a tremendous ambiguity because the chosen values of α, β matter!
Three particle degeneracy; 3 different eigenstates |ai, |bi, |ci give the following combinations

|ai(1) ⊗ |bi(2) ⊗ |ci(3) , |ai(1) ⊗ |ci(2) ⊗ |bi(3) ,

|bi(1) ⊗ |ci(2) ⊗ |ai(3) , |bi(1) ⊗ |ai(2) ⊗ |ci(3) ,
|ci(1) ⊗ |ai(2) ⊗ |bi(3) , |ci(1) ⊗ |bi(2) ⊗ |ai(3) .
154 CHAPTER 8. IDENTICAL PARTICLES

8.2.2 Permutation operators

Two particle systems
Consider the case when the vector space V relevant to the particles is the same for both
particles, even though the particles may be distinguishable. Call the particles 1 and 2.
Consider the state in which particle one is in state ui and particle 2 in state uj

|ui i(1) ⊗ |uj i(2) ∈ V ⊗ V (8.2.5)

Since the particles are possibly distinguishable note that

|ui i(1) ⊗ |uj i(2) 6= |uj i(1) ⊗ |ui i(2) . (8.2.6)

Define P̂21 the linear operator on V ⊗ V such that

h i
P̂21 |ui i(1) ⊗ |uj i(2) ≡ |uj i(1) ⊗ |ui i(2) . (8.2.7)

note that
P̂21 P̂21 = 1 , (8.2.8)
i.e. P̂21 is its own inverse. Claim

†
P̂21 = P̂21 , Hermitian (8.2.9)

Proof: First of all let’s recall that for a generic operator Ô, the adjoint of Ô is defined s.t.

hα|Ô† |βi = hβ|Ô|αi (8.2.10)

In our case, not writing the subscript labels,

 
huk | ⊗ hu` |P̂21 |ui i ⊗ |uj i = huk | ⊗ hu` | |uj i ⊗ |ui i = δkj δ`i
 ∗ h
i∗ h i∗
†
huk | ⊗ hu` |P̂21 |ui i ⊗ |uj i = hui | ⊗ huj |P̂21 |uk i ⊗ |u` i = hui | ⊗ huj | |u` i ⊗ |uk i = δi` δjk = δkj δ`i

hence
†
P̂21 = P̂21 X. (8.2.11)

Because of (8.2.8) we also have that P̂21 is unitary:

†
P̂21 P̂21 = P̂21 P̂21 = 1 . (8.2.12)

Given a generic state |ψi it is not clear a priori what would it be its behaviour under
the action of P̂21 , hence to make our life easier we want to rewrite a generic state |ψi in
8.2. IDENTICAL PARTICLES IN QUANTUM MECHANICS 155

terms of eigenstates of P̂21 .

We can define two eigenstates of P̂21 with the following properties
P̂21 |ψS i = |ψS i Symmetric state
P̂21 |ψA i = −|ψA i Antisymmetric state

and two operators Ŝ and Â

1 1
Ŝ ≡ (1 + P̂21 ) , Â ≡ (1 − P̂21 ) . (8.2.13)
2 2
Note that Ŝ and  are such that
1 1
P̂21 Ŝ = (P̂21 + P̂21 P̂21 ) = (P̂21 + 1) = Ŝ
2 2
1 1
P̂21 Â = (P̂21 − P̂21 P̂21 ) = (P̂21 − 1) = −Â
2 2
Therefore, given a generic state |ψi we have that
P̂21 Ŝ|ψi = Ŝ|ψi =⇒ Ŝ|ψi is symmetric
P̂21 Â|ψi = −Â|ψi =⇒ Â|ψi is anti-symmetric.

Because of this, the Hermitian operators Ŝ and  are called symmetric/antisymmetric

projectors. From a mathematical point of view Ŝ and  are orthogonal projectors2 and
satisfy
Ŝ 2 = Ŝ , Â2 = Â , Ŝ + Â = 1 , Ŝ Â = ÂŜ = 0 . (8.2.15)

Action on operators Let B(n) be an operator acting on the n-th vector space, i.e.
 
B(1)|ui i(1) ⊗ |uj i(2) = B|ui i ⊗ |uj i(2)
(1)
 
B(2)|ui i(1) ⊗ |uj i(2) = |ui i(1) ⊗ B|uj i
(2)

then the action of P̂21 on B(1) is

†
P̂21 B(1)P̂21 |ui i(1) ⊗ |uj i(2) = P̂21 B(1)|uj i(1) ⊗ |ui i(2)
   
= P̂21 B|uj i ⊗ |ui i(2) = |ui i(1) ⊗ B|uj i = B(2)|ui i ⊗ |uj i
(1) (2)
(8.2.16)
2
A projector P : V → U ⊂ V is orthogonal if V = ker P ⊕ range P , with ker P ⊥ range P . Take v ∈ V ,
then
Pv +v − Pv = u + w
v = |{z} (8.2.14)
| {z }
rangeP ker P
where w ∈ ker P , u = P v ∈ rangeP , then ker P ⊥ rangeP because
hw, ui = hw, P vi = hP † w, vi = hP w, vi = h0, vi = 0
156 CHAPTER 8. IDENTICAL PARTICLES

hence
†
P̂21 B(1)P̂21 = B(2) (8.2.17)
Similarly we have
†
P̂21 B(2)P̂21 = B(1) (8.2.18)
and if we consider a generic operator Θ̂(1, 2), then

†
P̂21 Θ̂(1, 2)P̂21 = Θ̂(2, 1) . (8.2.19)

Note that if Θ̂(1, 2) = Θ̂(2, 1) we say Θ̂(1, 2) is symmetric. If an operator is symmetric then
†
0 = P̂21 Θ̂(1, 2)P̂21 − Θ̂(1, 2)
0 = P̂21 Θ̂(1, 2) − Θ̂(1, 2)P̂21
0 = [P̂21 , Θ̂(1, 2)] (8.2.20)

[P̂21 , Θ̂(1, 2)] = 0 ⇐⇒ Θ̂ is symmetric . (8.2.21)

N particle systems
In a N particle system we can define N ! permutation operators P̂i1 ,...,iN , with P̂12...N being
the identity. For a 3-particle system, for example, the operator Pnpq acting on a state has
the effect of

n→1 n − th state moved to position 1

P̂npq means p→2 p − th state moved to position 2
q→3 q − th state moved to position 3

e.g.
P̂231 |ui i(1) ⊗ |uj i(2) ⊗ |uk i(3) = |uj i(1) ⊗ |uk i(2) ⊗ |ui i(3) (8.2.22)
You should check that its inverse is P̂312 , so that

P̂231 P̂312 = 1 . (8.2.23)

More formally we can define a permutation of N numbers by the function α that maps the
standard ordered integers 1, . . . , N into some arbitrary ordering of them

α : [1, 2, . . . , N ] → [α(1), α(2), . . . , α(N )] (8.2.24)

and associate it with a permutation operator

P̂α ≡ P̂α(1), α(2), ..., α(N ) (8.2.25)

P̂α |u1 i(1) ⊗ · · · ⊗ |uN i(N ) = |uα(1) i(1) ⊗ · · · ⊗ |uα(N ) i(N ) (8.2.26)
8.2. IDENTICAL PARTICLES IN QUANTUM MECHANICS 157

For example

P̂3142 |u1 i(1) ⊗ |u2 i(2) ⊗ |u3 i(3) ⊗ |u4 i(4) = |u3 i(1) ⊗ |u1 i(2) ⊗ |u4 i(3) ⊗ |u2 i(4) (8.2.27)

or
P̂3142 |ai(1) ⊗ |bi(2) ⊗ |ci(3) ⊗ |di(4) = |ci(1) ⊗ |ai(2) ⊗ |di(3) ⊗ |bi(4) (8.2.28)
The set of all permutations of N objects forms the symmetric group SN and it has N !
elements. For S3 we have 6 elements or the 6 permutation operators:
cyclic cyclic cyclic cyclic
P̂123 → P̂312 → P̂231 , P̂132 → P̂213 → P̂321
|{z} | {z }
1 these are transpositions,
a permutation in which only
2 particles are exchanged
without affecting the rest

P̂132 is a transposition in which the states of the second and third particles are exchanged
while the first particle is left unchanged. For transpositions we sometimes use the notation
where we just indicate the two labels that are being transposed. Those two labels could be
written in any order without risk of confusion, but we will use ascending order:

(12) ≡ P213
(13) ≡ P321 (8.2.29)
(23) ≡ P132

While all permutations that are transpositions are Hermitian (see the proof for P̂21 that
easily generalizes), general permutations are not Hermitian. It is intuitively clear that any
permutation can be written as product of transpositions: any set of integers can be reordered
into any arbitrary position by transpositions (in fact by using transpositions of consecutive
labels). The decomposition of a permutation into a product of transpositions is not unique,
but it is unique (mod 2). Hence we have that every permutation is either even or odd. A
permutation is said to be even if it is the product of an even number of transpositions, and
it is said to be odd if it is the product of an odd number of transpositions.
Since transposition operators are and unitary any permutation is a unitary operator. All
transpositions are also Hermitian, but an arbitrary product of them is not hermitian be-
cause the transpositions do not necessarily commute.

In fact, the Hermitian conjugate of a permutation is its inverse, which is a permutation

of the same parity. This is clear from writing P̂α as a product of transpositions Pti :

P̂α = P̂t1 P̂t2 . . . P̂tk

P̂α† = P̂t†k . . . P̂t†2 P̂t†1 = P̂tk . . . P̂t2 P̂t1 (8.2.30)

and therefore
=⇒ P̂α P̂α† = 1 (8.2.31)
158 CHAPTER 8. IDENTICAL PARTICLES

Theorem 8.2.1. The number of even permutations is the same as the number of odd
permutations
Proof. Consider the map that multiplies any permutation by (12) from the left (12) :
Peven → Podd so that if σ ∈ Peven then (12)σ ∈ Podd . This map is one to one

(12)σ = (12)σ 0 =⇒ σ = σ 0 , (8.2.32)

by multiplying from the left by (12), which is the inverse of (12). This map is also surjective
or onto:for any β ∈ Podd , we have β = (12) (12)β .
| {z }
∈Peven

A\B P̂312 P̂231 (23) (12) (13)

P̂312 P̂231 1 (12) (13) (23)
P̂231 1 P̂312 (13) (23) (12)
(23) (13) (12) 1 P̂231 P̂312
(12) (23) (13) P̂312 1 P̂231
(13) (12) (23) P̂231 P̂312 1

Table 8.1: A · B matrix for S3.

Complete symmetrizer and antisymmetrizer

Permutation operators do not commute, so we can’t find complete basis of states that are
eigenstates of all permutation operators. It is possible, however, to find some states that
are simultaneous eigenvectors of all permutation operators.
Consider N particles, each with the same vector space. Let P̂α be an arbitrary permutation,
then

Symmetric state |ψS i : P̂α |ψS i = |ψS i ∀α

Antisymmetric state |ψA i : P̂α |ψA i = α |ψA i

where (
+1 if P̂α is an even permutation
α = (8.2.33)
−1 if P̂α is an odd permutation
In the total Hilbert space V ⊗N ≡ V ⊗ · · · ⊗ V , we can identify a subspace SymN V ⊂ V ⊗N
| {z }
N
of symmetric states and a subspace AntiN V ⊂ V ⊗N of antisymmetric states. Can we
construct projectors into such subspaces?
Yes!
1 X 1 X
Ŝ ≡ P̂α and  ≡ α P̂α (8.2.34)
N! α N! α
8.2. IDENTICAL PARTICLES IN QUANTUM MECHANICS 159

where we sum over all N ! permutations. Ŝ is called the symmetrizer and  is called the
antisymmetrizer.
Claim: Ŝ = Ŝ †  = † (8.2.35)
Hermitian conjugation of P̂α gives P̂α−1 which is even if P̂α is even and odd if P̂α is odd.
Thus Hermitian conjugation just rearranges the sums, leaving them invariant.
Moreover
P̂α0 Ŝ = Ŝ P̂α0 = Ŝ (8.2.36)
P̂α0 Â = ÂP̂α0 = α0 Â (8.2.37)
Proof. Note that P̂α0 acting on the list of permutations simply rearranges the list, given
two permutations Pγ1 6= Pγ2 then P̂α0 Pγ1 6= P̂α0 Pγ2 , hence
1 X 1 X 1 X
P̂α0 Ŝ = P̂α0 P̂α = P̂α0 P̂α = P̂β = Ŝ X ( 8.2.38)
N! α N! α N!
β

analogously
1 X 1 X 1 X
P̂α0 Â = P̂α0 α P̂α = α P̂α0 P̂α = α α0 α0 P̂α0 P̂α
N! α N! α N! α | {z }
=1
α 0 X α 0 X
= α α0 P̂α0 P̂α = β P̂β = α0 Â X (8.2.39)
N! α N!
β

Finally they are projectors

Ŝ 2 = Ŝ , Â2 = Â , Ŝ Â = ÂŜ = 0 (8.2.40)

1 X 1 X 1
Ŝ 2 = P̂α Ŝ = Ŝ = N ! Ŝ = Ŝ X (8.2.41)
N! α N! α N!
1 X 1 X 1 X 1
Â2 = α P̂α Â = α α Â = Â = N ! Â = Â X (8.2.42)
N! α N! α N! α N!
1 X 1 X Ŝ X
ÂŜ = α P̂α Ŝ = α Ŝ = α = 0 X (8.2.43)
N! α N! α N! α
Since,
P as explained before there are equal numbers of even and odd permutations, i.e.

α α = 0.
Note that
Ŝ|ψi ∈ SymN V since P̂α Ŝ|ψi = Ŝ|ψi ∀ α (8.2.44)
and analogously
Â|ψi ∈ AntiN V since P̂α Â|ψi = α Â|ψi ∀ α (8.2.45)
Hence, they are, as claimed, projectors into the symmetric and antisymmetric subspaces:
Ŝ : V ⊗N → SymN V , Â : V ⊗N → AntiN V (8.2.46)
160 CHAPTER 8. IDENTICAL PARTICLES

Example: N = 3 For S3 we have 6 elements or the 6 permutation operators:

P̂123 = 1 , P̂312 , P̂231 , P̂132 , P̂213 , P̂321

In this case the symmetrizer and antisymmetrizer operators Ŝ and  are

Ŝ = 16 (1 + P̂312 + P̂231 + P̂132 + P̂213 + P̂321 ) (8.2.47)

 = 61 (1 + P̂312 + P̂231 − P̂132 − P̂213 − P̂321 ) (8.2.48)

Note that
Ŝ + Â = 13 (1 + P̂312 + P̂231 ) =
6 1 = P̂123 (8.2.49)

This is a manifestation of the fact that in general for N > 2, we have

SymN V ⊕ AntiN V ⊂ V ⊗N (8.2.50)

i.e. in principle, the N -particle Hilbert space is not spanned by purely symmetric or anti-
symmetric states.
We define Θ(1, 2, . . . , N ) to be a completly symmetric observable if

[Θ(1, 2, . . . , N ), P̂α ] = 0 ∀α (8.2.51)

8.3 The symmetrization postulate

In a system with N identical particles the states that are physically realized are not ar-
bitrary states in V ⊗N , but rather they are totally symmetric (i.e. belong to SymN V ), in
which case the particles are said to be bosons, or they are totally antisymmetric (i.e. belong
to AntiN V ) in which case they are said to be fermions.

Comments:

1. The above is a statement of fact in 3D. Alternative possibilities can happen in worlds
with 2 spatial dimensions (anyons)

2. The postulate describes the statistical behaviour of bosons and of fermions

3. Spin-statistics theorem from Quantum Field Theory shows that bosons are particles
of integer spins (0, 1, 2, . . . ) while fermions are particles of half-integer spin (1/2, 3/2
, ...)

4. The symmetrization postulate for elementary particles lead to a definite character, as

bosons or fermions, for composite particles, which in turn obey the symmetrization
8.3. THE SYMMETRIZATION POSTULATE 161

postulate. Take for example two hydrogen atoms

The system is made by 4 particles and its total wavefunction is Ψ(p1 , e1 ; p2 , e2 ). Since
the two electrons are identical particles of spin 1/2, the wavefunction must be anti-
symmetric under the exchange e1 ↔ e2

Ψ(p1 , e2 ; p2 , e1 ) = −Ψ(p1 , e1 ; p2 , e2 ) . (8.3.1)

Exactly the same argument applies to the protons,

Ψ(p2 , e1 ; p1 , e2 ) = −Ψ(p1 , e1 ; p2 , e2 ) . (8.3.2)

Therefore under the simultaneous exchange

Ψ(p2 , e2 ; p1 , e1 ) = +Ψ(p1 , e1 ; p2 , e2 ) . (8.3.3)

The exchange i n ( 8.3.3) corresponds t o p1 ↔p2 and e 1 ↔e 2, an exchange of t he t wo

hydrogen atoms! Since t he wavefunction i s s ymmetric under t his exchange, ( 8.3.3)
shows that the hydrogen atom is a boson!

5. The symmetrization postulate solves the exchange degeneracy problem.

Say |ui ∈ V ⊗N represents mathematically a state. Let V|ui ≡ span P̂α |ui , ∀α .


Depending on |ui the dimension of V|ui can go from 1 to N !. This dimensionality, if

different from one, is the degeneracy due to exchange.
The exchange degeneracy problem (i.e. the ambiguity in finding a representative for
the physical state in V|ui ) is solved by the symmetrization postulate by showing that
V|ui contains, up to scale, a single ket of SymN V and a single ket of AntiN V .

Proof. Suppose we have two states |ψi, |ψ 0 i ∈ V|ui that both happen to be symmetric:
|ψi, |ψ 0 i ∈ SymN V . We can write them as
X X
|ψi = cα Pα |ui and |ψ 0 i = c0α Pα |ui (8.3.4)
α α
162 CHAPTER 8. IDENTICAL PARTICLES

with cα , c0α some coefficients. Then, since |ψi ∈ SymN V

X X X X
|ψi = Ŝ|ψi = Ŝ cα Pα |ui = cα ŜPα |ui = cα Ŝ|ui = Ŝ|ui cα . (8.3.5)
α α α α

Analogously X
|ψ 0 i = Ŝ|ui c0α . (8.3.6)
α

Hence |ψi ∝ |ψ 0 i, the states are the same up to scale.

6. Building antisymmetric states.

Constructing the three-particle state Â|ui with |ui ∈ V ⊗3 given by

|ui = |ϕi(1) ⊗ |χi(2) ⊗ |ωi(3) (8.3.7)

The claim is that the antisymmetric state is constructed by a determinant:

|ϕi(1) |ϕi(2) |ϕi(3)

X
1 1
Â|ui = 3! α P̂α |ϕi(1) ⊗ |χi(2) ⊗ |ωi(3) = 3! |χi(1) |χi(2) |χi(3) (8.3.8)
α
|ωi(1) |ωi(2) |ωi(3)

When writing the products in the determinant one must reorder each term to have
the standard order |· i(1) ⊗ |· i(2) ⊗ |· i(3) . You can confirm you get the right answer.
Now do it generally. Recall the formula for the determinant of a matrix
X
det B̂ = α Bα(1),1 Bα(2),2 . . . Bα(N ),N (8.3.9)
α

Let |ωi be a generic state ∈ V ⊗N

|ωi = |ω1 i(1) |ω2 i(2) . . . |ωN i(N ) (8.3.10)

then
P̂α |ωi = |ωα(1) i(1) |ωα(2) i(2) . . . |ωα(N ) i(N ) (8.3.11)
so that
1 X 1 X
Â|ωi = α P̂α |ωi = α |ωα(1) i(1) |ωα(2) i(2) . . . |ωα(N ) i(N ) . (8.3.12)
N! α N! α

If we define a matrix
ωij ≡ |ωi i(j) (8.3.13)
then
1 X 1
Â|ωi = α ωα(1),1 ωα(2),2 . . . ωα(N ),N = det(ω) (8.3.14)
N! α N!
8.4. OCCUPATION NUMBERS 163

i.e.
|ω1 i(1) |ω1 i(2) . . . |ω1 i(N )

|ω2 i(1) |ω2 i(2) . . . |ω2 i(N )

1
Â|ωi = (8.3.15)
N! .. ..
. .

|ωN i(1) ... ... |ωN i(N )

8.4 Occupation numbers

Consider a system of N identical particle. Basis states in V ⊗N take the form

|ui i(1) ⊗ . . . |up i(N ) (8.4.1)

where the one-particle states form an orthonormal basis of V :

V = span{|u1 i, |u2 i, . . . } (8.4.2)

By applying Ŝ or  to the full set of states in V ⊗N we obtain all physical states in SymN V
and AntiN V . But many different states in V ⊗N can give rise to the same state in SymN V
and AntiN V after the application of the projectors.
To distinguish basis states in V ⊗N that after application of Ŝ or  are linearly indepen-
dent, define the occupation number. We assign a set of occupation numbers to a basis state
|·i ⊗ · · · ⊗ |·i. An occupation number is an integer ni ≥ 0 associated with each vector in V :

|u1 i , |u2 i , . . . , |uk i , . . . (8.4.3)

n1 n2 nk

We define nk to be the number of times that |uk i appears in the chosen basis state
|·i ⊗ · · · ⊗ |·i. Thus, by inspection of the state |·i ⊗ · · · ⊗ |·i we can read all the occu-
pation numbers n1 , n2 , · · · . It should be clear that the action of a permutation operator on
a basis state in V ⊗N will not change the occupation numbers.

Two basis states in V ⊗N with the same occupation numbers can be mapped into each
other by a permutation operator; they lead to the same state in SymN V and to the same
state (up to a sign) in AntiN V . Two basis states in V ⊗N with different occupation numbers
cannot be mapped into each other by a permutation operator. They must lead to different
states in SymN V and to different states in AntiN V , unless they give zero.

Given the occupation numbers of a basis state, we denote the associated basis state in
SymN V as follows
|n1 , n2 , . . . iS ni ≥ 0 (8.4.4)
164 CHAPTER 8. IDENTICAL PARTICLES

Explicitly
|n1 , n2 , . . . iS ≡ cS Ŝ |u1 i . . . |u1 i ⊗ |u2 i . . . |u2 i ⊗ . . . (8.4.5)
| {z } | {z }
n1 times n2 times
where cS is a constant that is used to give the state unit normalization. More briefly we
write
|n1 , n2 , . . . iS ≡ cS Ŝ |u1 i⊗n1 ⊗ |u2 i⊗n2 ⊗ . . . (8.4.6)
where |ui i⊗ni is equal to 1 when ni = 0 These states form an orthonormal basis in SymN V :
0
S hn1 , n02 , . . . |n1 , n2 , . . . iS = δn1 ,n01 δn2 ,n02 . . . (8.4.7)

The space SymN V relevant to identical bosons is spanned by all the states
X
|n1 , n2 , . . . i with nk = N (8.4.8)
k

The space AntiN V relevant to identical fermions is spanned by all the states
X
|n1 , n2 , . . . iA with nk = N and nk ∈ {0, 1} , (8.4.9)
k

since occupation numbers cannot be greater than one (any state with an occupation number
two or larger is killed by Â). We have
|n1 , n2 , . . . iA ≡ cA Â |u1 i⊗n1 ⊗ |u2 i⊗n2 ⊗ . . . (8.4.10)
where cA is a constant that is used to give the state unit normalization. These states form
an orthonormal basis in AntiN V .

8.5 Particles that live in V ⊗ W

A particle may have space degrees of freedom, described by a vector space V and spin degree
of freedom associated with W . Suppose we have a state than of 2 such particles described
in (V ⊗ W )⊗2 for example
|ψi = |vi i(1) ⊗ |wi i(1) ⊗ |vj i(2) ⊗ |wj i(2) + . . . (8.5.1)

This ψ should belongs either to Sym2 (V ⊗ W ) or to Anti2 (V ⊗ W ). The permutation

operator here that exchange particles 1 and 2 is
 
P̂3412 |ψi = P̂3412 |vi i(1) ⊗|wi i(1) ⊗|vj i(2) ⊗|wj i(2) = |vj i(1) ⊗|wj i(1) ⊗|vi i(2) ⊗|wi i(2) ( 8.5.2)

Wanto to express this in terms of Sym2 V , Anti2 V , Sym2 W , Anti2 W .

Why? Because it is possible: for any state
W W 1  1 
. . . |ai . . . |bi = . . . |ai . . . |bi + . . . |bi . . . |ai + . . . |ai . . . |bi − . . . |bi . . . |ai (8.5.3)
2| {z } 2| {z }
∈ Sym2 W ∈ Anti2 W
8.5. PARTICLES THAT LIVE IN V ⊗ W 165

Thus we can assume we work with simultaneous eigenstates of P̂3214 , which exchanges the
V states, and of P̂1432 , which exchanges the W states. Note that

P̂3412 = P̂3214 P̂1432 (8.5.4)

where the order is not important since [P̂3214 , P̂1432 ] = 0.

The eigenvalues are

P̂3214 P̂1432 P̂3412

1 1 1
−1 −1 1
1 −1 −1
−1 1 −1

This means that

Sym2 (V ⊗ W ) ' Sym2 V ⊗ Sym2 W ⊕ Anti2 V ⊗ Anti2 W

(8.5.5)
Anti2 (V ⊗ W ) ' Sym2 V ⊗ Anti2 W ⊕ Anti2 V ⊗ Sym2 W



(8.5.6)

where with ' we indicate

|vi i(1) ⊗ |wi i(1) ⊗ |vj i(2) ⊗ |wj i(2) ' |vi i(1) ⊗ |vj i(1) ⊗ |wi i(2) ⊗ |wj i(2) . (8.5.7)

The generalization to 2 particle belonging to (U ⊗ V ⊗ W ) is simple, for 3 or more particle

is more complicated.

Example. Two electrons with spin wavefunction

Ψ(x1 , m1 ; x1 , m2 ) = φ(x1 , x2 ) · χ(m1 , m2 ) Ŝz = m~ (8.5.8)

χ can be some normalized state in the space spanned by the triplet and the singlet. The
probability dP to find one electron in d3 x1 around x1 and in d3 x2 around x2 is

dP = |φ(x1 , x2 )|2 d3 x1 d3 x2 (8.5.9)

Assume for simplicity that the electrons are non interacting so that the Schrödinger equation

~2 2 ~2 2
 
− ∇ + V (x1 ) − ∇ + V (x2 ) Ψ = EΨ (8.5.10)
2m x1 2m x2

is separable, so there is a solution of the form ψA (x1 )ψB (x2 ) with

Z Z Z
3 2 3 2 ∗
d x |ψA (x)| = 1 , d x |ψB (x)| = 1 , d3 x ψA 6 0
(x)ψB (x) = αAB =
(8.5.11)
166 CHAPTER 8. IDENTICAL PARTICLES
p p
By Schwarz’s inequality |hu, vi| ≤ hu, ui hv, vi we have
Z
∗
p p
d3 x ψA (x)ψB (x) = |hψA , ψB i| ≤ |hψA , ψA i| |hψB , ψB i| =⇒ |αAB | ≤ 1 (8.5.12)

But then must build

N±

φ± (x1 , x2 ) = √ ψA (x1 )ψB (x2 ) ± ψA (x2 )ψB (x1 ) (8.5.13)
2
with N± a real normalization constant.

Take the following combination of φ and χ:

φ+ · χsinglet so that the total wavefunction is antisymmetric

φ− · χtriplet any of the 3 states of the triplet

Again, the probability to find one electron in d3 x1 around x1 and in d3 x2 around x2 is

dP± = |φ± (x1 , x2 )|2 d3 x1 d3 x2

N± n  ∗ ∗
o
= √ |ψA (x1 )ψB (x2 |2 + |ψA (x2 )ψB (x1 )|2 ± 2< ψA (x1 )ψA (x2 )ψB (x2 )ψB (x1 ) d3 x1 d3 x2
2 | {z }
Exchange density
(8.5.14)

If we take the case x1 = x2 = x, we get

n o
dP± = N± |ψA (x)ψB (x)|2 ± |ψA (x)ψB (x)|2 d3 x1 d3 x2
=⇒ dP+ = 2N± |ψA (x)ψB (x)|2 d3 x1 d3 x2 (8.5.15)
dP− = 0 (8.5.16)

Recall that P+ is associated with the singlet, while P− with the triplet. Therefore electrons
avoid each other in space when they are in the triplet state. In the singlet states there is
enhanced probability to be at the same point.
Note that normalization requires

N±2
Z n  ∗ ∗
o
1= d3 x1 d3 x2 |ψA (x1 )ψB (x2 |2 + |ψA (x2 )ψB (x1 )|2 ± 2< ψA (x1 )ψA (x2 )ψB (x2 )ψB (x1 )
2
N±2
 Z Z 
3 ∗ 3 ∗
= 1 + 1 ± 2< d x1 ψA (x1 )ψB (x1 ) d x2 ψB (x2 )ψA (x2 )
2
n o
∗
= N±2 1 ± < [αAB · αAB ]
  1
= N±2 2
1 ± |αAB | =⇒ N± = p (8.5.17)
1 ± |αAB |2
8.6. COUNTING STATES AND DISTRIBUTIONS 167

So
2
dP+ = |ψA (x)ψB (x)|2 d3 x1 d3 x2 (8.5.18)
1 ± |αAB |2

to be compared with
dPD = |ψA (x)|2 |ψB (x)|2 d3 x1 d3 x2 (8.5.19)

for distinguishable particles.

Since from (8.5.12) we have |αAB < 1|, then

dP+ ≥ dPD (8.5.20)

Assume ψA (x) is nonzero only in a region RA , ψB (x) is nonzero only in a region RB and
RA ∩ RB = 0, then
Z
∗
αAB = d3 x ψA (x)ψB (x) = 0 (8.5.21)

since ψA requires x ∈ RA and ψB requires x ∈ RB . Therefore in this case N± = 1.

Then the probability to find an electron in d3 x1 around x1 ∈ RA and another in d3 x2
around x2 ∈ RB is
n  ∗ ∗
dP± = |ψA (x1 )ψB (x2 |2 + | )|2 ± 2< ψA ) d3 x1 d3 x2

ψA(x )
2ψB(x
1 (x1 )
ψA(x )ψB
2 (x2 )
ψB(x
1

= |ψA (x)|2 |ψB (x)|2 d3 x1 d3 x2 = dPD (8.5.22)

it is the probability density for distinguishable particles.

Therefore, there is no need to symmetrize or antisymmetrize the wavefunction of non over-
lapping localized particles.

8.6 Counting states and distributions

Ei energy of the i-th level, di degeneracy of the i-th level. Assume we have N particles
and we want to place N1 particles in level 1, . . . , Ni particles in level i (Ei , di ). Let’s call
Q(N1 , N2 , . . . ) the number of ways to do this.
168 CHAPTER 8. IDENTICAL PARTICLES

8.6.1 Distinguishable particles (Maxwell Boltzman)

N!
Split N into N1 , N2 , . . . in N1 !N2 !... ways (imagine putting them on a line |{z}
. . . |{z}
. . . after
N1 N2
drawing one ball at a time). Placing Ni particles in di slots gives (di )Ni ways, therefore

Y (di )Ni
Q(N1 , N2 , . . . ) = N ! Maxwell Boltzman
Ni !
i

8.6.2 Identical fermions

Splitting the N states into groups for identical particles can only be done in one way

Ni < di

how many ways to place them?

di
di choose Ni =
Ni !(di − Ni )!
Y di
=⇒ Q(N1 , N2 , . . . ) =
Ni !(di − Ni )!
i

8.6.3 Identical bosons

Ni particles!

Ni balls and (di − 1) bars,

for example:

How many ways to order the Ni + di − 1 objects? (Ni + di − 1)! but we must divide by the
irrelevant permutations, hence
Y (Ni + di − 1)!
Q(N1 , N2 , . . . ) = (8.6.1)
Ni !(di − 1)!
i

This is for bosons:

Q(N
P 1 , N2 , . . . ) counts the number of ways to have N particles and fixed energy E =
i Ni Ei . Want to find the values of N1 , N2 , . . . that are most likely.
P P
Want to maximize Q(N1 , N2 , . . . ) under the constraint that N = i Ni and E = i Ni Ei .
Maximizing Q is the same as maximizing ln Q and using lagrange multipliers
X X
f (N1 , N2 , . . . ) = ln Q(N1 , N2 , . . . ) + α(N − Ni ) + β(E − Ni Ei ) (8.6.2)
i i
8.6. COUNTING STATES AND DISTRIBUTIONS 169

Do the fermion one, using QF from (8.6.1) we have

X
ln QF = ln di ! − ln Ni ! − ln(di − Ni )! (8.6.3)
i

Since all these quantities di , Ni are large we can use the Stirling approximation

ln n! ' n ln n − n (8.6.4)

so that
X X
ln QF = di ln di −di −Ni ln Ni +
i −(di −Ni ) ln(di −Ni )+di −
N N
i = di ln di −Ni ln Ni −(di −Ni ) ln(di −Ni )
i i
(8.6.5)
Minimizing w.r.t. to Ni without constraints,
 
d di − Ni
ln QF = − ln Ni − 1
+ ln(di − Ni ) + 1
= ln . (8.6.6)
dNi Ni
so that, adding the lagrange multipliers, we have
 
∂f di − Ni di − Ni  
= ln − α − βEi =⇒ = eα+βEi =⇒ di = Ni eα+βEi + 1
∂Ni Ni Ni
di
=⇒ Ni = α+βE
(8.6.7)
+1 e i
P P
α and β can be calculated using the equations i Ni = N and i Ni Ei = E:
µ(T ) 1
α≡− , β≡ definition of temperature (8.6.8)
kB T kB T
then
di
Ni = Ei −µ(T )
(8.6.9)
e kB T
+1
Ni
The expected occupation number n ∼ di for a single state is
 E−µ(T )
−1
n= e kB T
+1 Fermi-Dirac distribution

For bosons we have

 E−µ(T ) −1
n= e kB T
−1 Bose-Einstein distribution

Since n ≥ 0 we need E > µ for all energy levels µ < Ei ∀i. For an ideal gas µ(T ) < 0 ∀T ,
i.e. α > 0
For fermions
170 CHAPTER 8. IDENTICAL PARTICLES

Figure 8.3: Occupation number for a state as a function of the energy for a system of identical
fermions in the T → 0 limit. µ(T = 0) = EF is called the Fermi energy.

Figure 8.4: Chemical potential µ as a function of the temperature for a system of identical
bosons. TC , the critical temperature is defined to be the temperature such that µ(TC ) = 0
and it’s the temperature for Bose-Einstein condensation

Figure 8.5: Chemical potential µ as a function of the temperature for a system of identical
fermions.

Aside from statistical mechanics

∂E
µ= keeping constant entropy may require lowering the energy (8.6.10)
∂N S,V

Suppose we add a particle with no energy to the system. S will increase (more ways to
8.6. COUNTING STATES AND DISTRIBUTIONS 171

divide up the total energy) for this not to happen, must reduce the energy.

dE(V, S) = T dS − P dV + µdN
= d(T S) − SdT − P dV (8.6.11)
d (E − T S) = −SdT − P dV + µdN
| {z }

F (T, V ) = E − T S . (8.6.12)

µ is an intensive quantity, and in terms of F we have

∂F Adding a particle changes

µ= the energy and the entropy (8.6.13)
∂N T,V
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8.06 Quantum Physics III

Spring 2018

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