Perturbation theory (quantum mechanics)

In quantum mechanics, perturbation theory is a set of exact, but they can lead to accurate results as long as the
approximation schemes directly related to mathematical expansion parameter, say , is very small. Typically, the
perturbation for describing a complicated quantum sys- results are expressed in terms of nite power series in
tem in terms of a simpler one. The idea is to start with that seem to converge to the exact values when summed
a simple system for which a mathematical solution is to higher order. After a certain order n ~ 1/ however,
known, and add an additional perturbing Hamiltonian the results become increasingly worse since the series are
representing a weak disturbance to the system. If the usually divergent (being asymptotic series). There exist
disturbance is not too large, the various physical quanti- ways to convert them into convergent series, which can be
ties associated with the perturbed system (e.g. its energy evaluated for large-expansion parameters, most eciently
levels and eigenstates) can be expressed as corrections by Variational method.
to those of the simple system. These corrections, be- In the theory of quantum electrodynamics (QED), in
ing small compared to the size of the quantities them- which the electronphoton interaction is treated pertur-
selves, can be calculated using approximate methods such batively, the calculation of the electrons magnetic mo-
as asymptotic series. The complicated system can there- ment has been found to agree with experiment to eleven
fore be studied based on knowledge of the simpler one. decimal places.[1] In QED and other quantum eld the-
ories, special calculation techniques known as Feynman
diagrams are used to systematically sum the power series
1 Approximate Hamiltonians terms.

Perturbation theory is an important tool for describing

real quantum systems, as it turns out to be very di- 2.1 Limitations
cult to nd exact solutions to the Schrdinger equation for
Hamiltonians of even moderate complexity. The Hamil- 2.1.1 Large perturbations
tonians to which we know exact solutions, such as the
hydrogen atom, the quantum harmonic oscillator and the Under some circumstances, perturbation theory is an in-
particle in a box, are too idealized to adequately describe valid approach to take. This happens when the system
most systems. Using perturbation theory, we can use the we wish to describe cannot be described by a small per-
known solutions of these simple Hamiltonians to generate turbation imposed on some simple system. In quantum
solutions for a range of more complicated systems. chromodynamics, for instance, the interaction of quarks
with the gluon eld cannot be treated perturbatively at low
energies because the coupling constant (the expansion pa-
rameter) becomes too large.
2 Applying perturbation theory
Perturbation theory is applicable if the problem at hand 2.1.2 Non-adiabatic states
cannot be solved exactly, but can be formulated by adding
a small term to the mathematical description of the ex- Perturbation theory also fails to describe states that are
actly solvable problem. not generated adiabatically from the free model, includ-
ing bound states and various collective phenomena such
For example, by adding a perturbative electric potential as solitons. Imagine, for example, that we have a sys-
to the quantum mechanical model of the hydrogen atom, tem of free (i.e. non-interacting) particles, to which an
tiny shifts in the spectral lines of hydrogen caused by the attractive interaction is introduced. Depending on the
presence of an electric eld (the Stark eect) can be cal- form of the interaction, this may create an entirely new
culated. This is only approximate because the sum of a set of eigenstates corresponding to groups of particles
Coulomb potential with a linear potential is unstable (has bound to one another. An example of this phenomenon
no true bound states) although the tunneling time (decay may be found in conventional superconductivity, in which
rate) is very long. This instability shows up as a broad- the phonon-mediated attraction between conduction elec-
ening of the energy spectrum lines, which perturbation trons leads to the formation of correlated electron pairs
theory fails to reproduce entirely. known as Cooper pairs. When faced with such systems,
The expressions produced by perturbation theory are not one usually turns to other approximation schemes, such

1
2 3 TIME-INDEPENDENT PERTURBATION THEORY

as the variational method and the WKB approximation. are associated with the unperturbed system. Note the use
This is because there is no analogue of a bound parti- of braket notation.
cle in the unperturbed model and the energy of a soliton We now introduce a perturbation to the Hamiltonian. Let
typically goes as the inverse of the expansion parameter. V be a Hamiltonian representing a weak physical distur-
However, if we integrate over the solitonic phenomena, bance, such as a potential energy produced by an external
the nonperturbative corrections in this case will be tiny; eld. (Thus, V is formally a Hermitian operator.) Let
of the order of exp(1/g) or exp(1/g2 ) in the perturba- be a dimensionless parameter that can take on values
tion parameter g. Perturbation theory can only detect so- ranging continuously from 0 (no perturbation) to 1 (the
lutions close to the unperturbed solution, even if there
full perturbation). The perturbed Hamiltonian is
are other solutions for which the perturbative expansion
is not valid.

H = H0 + V
2.1.3 Dicult computations
The energy levels and eigenstates of the perturbed Hamil-
The problem of non-perturbative systems has been some- tonian are again given by the Schrdinger equation:
what alleviated by the advent of modern computers.
It has become practical to obtain numerical non-
perturbative solutions for certain problems, using meth- (H0 + V ) |n = En |n.
ods such as density functional theory. These advances
have been of particular benet to the eld of quantum Our goal is to express E and |n in terms of the energy
chemistry. Computers have also been used to carry out levels and eigenstates of the old Hamiltonian. If the per-
perturbation theory calculations to extraordinarily high turbation is suciently weak, we can write them as power
levels of precision, which has proven important in particle series in :
physics for generating theoretical results that can be com-
pared with experiment.
En = En(0) + En(1) + 2 En(2) +
  
  
3 Time-independent perturbation |n = n(0) + n(1) + 2 n(2) +

theory where

Time-independent perturbation theory is one of two cat-

egories of perturbation theory, the other being time- 1 dk En
En(k) =
dependent perturbation (see next section). In time- k! dk
independent perturbation theory the perturbation Hamil-  1 dk |n
 (k)
tonian is static (i.e., possesses no time dependence). n =
k! dk
Time-independent perturbation theory was presented by
Erwin Schrdinger in a 1926 paper,[2] shortly after he When = 0, these reduce to the unperturbed values,
produced his theories in wave mechanics. In this paper which are the rst term in each series. Since the perturba-
Schrdinger referred to earlier work of Lord Rayleigh,[3] tion is weak, the energy levels and eigenstates should not
who investigated harmonic vibrations of a string per- deviate too much from their unperturbed values, and the
turbed by small inhomogeneities. This is why this terms should rapidly become smaller as we go to higher
perturbation theory is often referred to as Rayleigh order.
Schrdinger perturbation theory. Substituting the power series expansion into the
Schrdinger equation, we obtain
3.1 First order corrections
(  ) (
 (0)  (1)
[4]
We begin with an unperturbed Hamiltonian H 0 , which (H 0 + V ) n + n + = En(0) + En(1) + 2 En(2) +
is also assumed to have no time dependence. It has
known energy levels and eigenstates, arising from the Expanding this equation and comparing coecients
time-independent Schrdinger equation: of each power of results in an innite series of
simultaneous equations. The zeroth-order equation is
simply the Schrdinger equation for the unperturbed sys-
 
 (0) (0)  (0) tem. The rst-order equation is
H0 n = En n , n = 1, 2, 3,

For simplicity, we have assumed that the energies are dis-    

 (1)   
crete. The (0) superscripts denote that these quantities H0 n + V n(0) = En(0) n(1) + En(1) n(0)
3.2 Second-order and higher corrections 3

Operating through by n(0) | . The rst term on the left- where the |k (0) are in the orthogonal complement of
hand side cancels the rst term on the right-hand side. |n(0) . The rst-order equation may thus be expressed
(Recall, the unperturbed Hamiltonian is Hermitian). This as
leads to the rst-order energy shift:
( )   
    (0)  
  En(0) H0 n(1) = k k (0)  V n(0)
En(1) = n(0)  V n(0) k=n

This is simply the expectation value of the perturbation For the moment, suppose that the zeroth-order energy
Hamiltonian while the system is in the unperturbed state. level is not degenerate, i.e. there is no eigenstate of
This result can be interpreted in the following way: sup- H 0 in the orthogonal complement of |n(0) with the en-
pose the perturbation is applied, but we keep the system (0)
ergy En . After renaming the summation dummy in-
in the quantum state |n(0) , which is a valid quantum dex above as k , we can pick any k = n , and multiply
state though no longer an energy eigenstate. The per- through by k (0) | giving
turbation causes the average energy of this state to in-
crease by n(0) |V |n(0) . However, the true energy shift
is slightly dierent, because the perturbed eigenstate is ( )   
(0)   
not exactly the same as |n(0) . These further shifts are En(0) Ek k (0) n(1) = k (0)  V n(0)
given by the second and higher order corrections to the
energy. We see that the above k (0) |n(1) also gives us the com-
ponent of the rst-order correction along |k (0) .
Before we compute the corrections to the energy eigen-
state, we need to address the issue of normalization. We Thus in total we get,
may suppose

  k (0)  V n(0) 
  (1)  (0)
n(0)  n(0) = 1, n = (0) (0)
k
k=n En Ek

but perturbation theory assumes we also have n|n = 1

The rst-order change in the n-th energy eigenket has
. It follows that at rst order in , we must have
a contribution from each of the energy eigenstates k
n. Each term is proportional to the matrix element
(  ) (  )
    k (0) |V |n(0) , which is a measure of how much the per-
n(0)  + n(1)  n(0) + n(1) =1
turbation mixes eigenstate n with eigenstate k; it is also
  inversely proportional to the energy dierence between
 
n(0)  n(1) + n(1)  n(0) = 0. eigenstates k and n, which means that the perturbation de-
Since the overall phase is not determined in quantum forms the eigenstate to a greater extent if there are more
mechanics, without loss of generality, we may assume eigenstates at nearby energies. We see also that the ex-
n(0) |n is purely real. Therefore, pression is singular if any of these states have the same
energy as state n, which is why we assumed that there is
  no degeneracy.
(0)  (1) (0)  (1)
n n = n n ,

and we deduce 3.2 Second-order and higher corrections

 We can nd the higher-order deviations by a similar pro-

 cedure, though the calculations become quite tedious with
n(0)  n(1) = 0.
our current formulation. Our normalization prescription
To obtain the rst-order correction to the energy eigen- gives that
state, we insert our expression for the rst-order energy
correction back into the result shown above of equating
 
the rst-order coecients of . We then make use of the 2 n(0)  n(2) + n(1)  n(1) = 0.
 
resolution of the identity,
Up to second order, the expressions for the energies and

    ( (normalized)
)  eigenstates
are:
 (0) (0)   (0)  (0) (0)   (0)
V n = k (0)
k  V n + n n  V n
k=n    
       k (0)  V n(0) 2
(0)   (0) (1)  (0) (0)   (0)
= k (0)
k  V n + En n , En () = En + n  V n
(0)
+2
(0) (0)
+O(3 )
k=n k=n En E k
4 3 TIME-INDEPENDENT PERTURBATION THEORY

  k (0)  V n(0)  (0)  V (0) (0)  V n(0)

 (0) (0) ( k )( )
|n() = n + k (0)
(0) (0)
+ 2
k
k=n E n E k k=n =n V k nE
(0)
n
(0) E
(0)
E
(0)
n E
(0)
|n(1) = 1 |k1 k

 n(0)  V n(0) k (0)  V n(0) E1nk1  n(0)  V k (0) k (0)  V n(0)

(  )
2 k (0) ( )2 2 n(0) + O(3 ).
(0) (0) 2 1 2 Vk2 n
V k k Vnn Vk1 n( (0)(0) (0)1)V2nk1 Vk1 n (0)
k=n En Ek |n =
(2)
k
=n 2 En|k1 Ek |n
Enk1 Enk2 Enk 2 Ek21 n
[
1
( )
Extending the process further, the third-order energy cor- Vk1 k2 Vk2 k3 Vk3 n Vnn Vk1 k2 Vk2 n 1 1 |V
rection can be shown to be [5] |n (3)
= + +
Ek1 n Enk2 Enk3 Ek1 n Enk2 Enk1 Enk2
[
Vk1 k2 Vk2 k3 Vk3 k4 Vk4 k2 + Vk3 k2 Vk1 k2 Vk4 k3 Vk2 k4 Vk k Vk k
|n(4) = 2 2 3 3
n(0) |V |m(0) m(0) |V |k (0) k (0) |V |n(0) |n(0)k|V1 n|mk(0)
2E E E
|2 k2 k4
2 k3
Ek1 n Ek2 n
En(3) = ( )( ) n(0) |V |n(0) ( )
( (0) 2 . )
k=n m=n
(0)
Em En
(0) (0)
Ek En
(0)
Vnn Vkm1 k=
2nVk3 E
nV
(0)
mk2 k3 En 1 1 1 |Vk2 n |2 Vk
+ + + +
Ek1 n Enk3 Ek2 n Enk3 Ek2 n Ek1 n Enk2 Ek1
( ) ]
Corrections to fth order (energies) and fourth order |Vnn |2 Vk1 n Vnn Vk1 k2 Vk2 n |Vk1 k2 |2 Vnn Vk1 n (0)
(states) in compact notation + + |k1
Ek1 n Ek31 n Ek32 n Ek1 n Ek31 k2
( ) (
If we introduce the notation, Vk1 n Vk2 k1 Vk3 k2 Vnk3 Vnn Vnk2 |Vnk1 |2 3|Vnk2 |2
2 + +
Ek1 n Enk2 Enk3 Enk2 Ek21 n 4Ek22 n

All terms involved k should be summed over k such that

Vnm n(0) |V |m(0) the denominator does not vanish.

Enm En(0) Em
(0)
3.3 Eects of degeneracy
then the energy corrections to fth order can be written
Suppose that two or more energy eigenstates are
degenerate. The rst-order energy shift is not well de-
ned, since there is no unique way to choose a basis
En(1) = Vnn of eigenstates for the unperturbed system. The various
|Vnk2 |2 eigenstates for a given energy will perturb with dier-
En(2) = ent energies, or may well possess no continuous family of
Enk2
perturbations at all. This is manifested in the calculation
Vnk3 Vk3 k2 Vk2 n |Vnk |2 of the perturbed eigenstate via the fact that the operator
En(3) = Vnn 2 3
Enk2 Enk3 Enk3
Vnk4 Vk4 k3 Vk3 k2 Vk2 n |Vnk4 |2 |Vnk2 |2 Vnk4 Vk4 k3 Vk3 n Vnk4 Vk4 k2 Vk2 n 2 |Vnk4 |
2
En(4) = Vnn Vnn + V
nk3
nn
Enk2 Enk3 Enk4 2
Enk 4
Enk2 EEn(0)
2 EH
nk04 Enk2 Enk2
4
3
Enk 4

Vnk4 Vk4 k3 Vk3 k2 Vk2 n |Vnk |2 Vnk4 Vk4 k3 Vk3 n 2 |Vnk4 | inverse.
2
= En(2) 2 4 2Vnn does
2
not have+a Vwell-dened
nn 3
Enk2 Enk3 Enk4 Enk4 Enk3 Enk4 Enk4
Let 2D denote the subspace spanned by these degener-
Vnk5 Vk5 k4 Vk4 k3 Vk3 k2 Vk2 n Vnk5 Vk5 k4 Vk4 n |Vnk
ate2 | eigenstates.
Vnk5 Vk5 kNo 2 n |Vnkhow
2 Vkmatter 2|
2
|Vnkthe
small 5| V
2
nk3 Vk3 k2 Vk2 n
perturbation
(5)
En = 2 E 2 2
Enk2 Enk3 Enk4 Enk5 Enk 4
nk5 Eis, Enk2 Enk
nk2in the degenerate Enk
5 subspace2 D the energy
Enk 5
Enk2 Enk3
dierences
Vnk5 Vk5 k4 Vk4 k3 Vk3 n Vnk5 Vk5 k4 Vk4 kbetween
2 Vk2 n
the eigenstates
Vnk5 Vk5 k3HV0k3are k2 Vzero,
k2 n so complete|Vnk5 |2 mix-
|Vnk3 |2 |Vnk |
Vnn 2 Vnn 2 ing of least
at Vnn some of these2 states +is Vassured.
nn 2 Typi-2 + 2Vnn 3 5
Enk3 Enk4 Enk5 Enk2 Enk4 Enk5 Enk2 Enk3 Enk5 Enk5 Enk3 Enk5
cally the eigenvalues will split and 2 the eigenspaces will
2 Vnk5 Vk5 k4 Vk4 n 2 Vnk5 Vk5 k3 Vk3 n 2 Vnk5 V k5 k2 Vk2 n 3 |Vnk5 | or at least get smaller
+ Vnn 3 E + Vnn 2 E2 + Vbecome
nn
simple 3 Vnn
(one-dimensional), 4
Enk 4
nk5 E nk3 nk5 dimensionE E
nk2 than nk5D. The successful Enk 5 perturbations will not

Vnk5 Vk5 k4 Vk4 k3 Vk3 k2 Vk2 n V V V be

nk5 k5 k4 k4 n |V
small nk5 | 2
relative
V to
V a poorly
nk3 k3 k2 k2 n V chosen basis of D. Instead,
= 2En(2) 2 we
consider2 the perturbation small if the new eigenstate
Enk2 Enk3 Enk4 Enk5 Enk4 Enk5 Enk5 Enk2 Enk3
( is close to the subspace D. The new Hamiltonian ) must be
Vnk5 Vk5 k4 Vk4 k3 Vk3 n Vnk5 Vk5 k4 Vk4 kdiagonalized
2 Vk2 n |Vnk in |2 |V
5D, ornka |2 variation
3slight (2) |Vnkof 5 |D, so to speak.
2
2Vnn 2 E 2 E + 2 2 + 2En 3
Enk nk4 Enk5 Enk2 Enk 4 These
nk5 correct Enk Enk
perturbed 3eigenstates in D
Enk are
5 now the basis
(
3
) for the perturbation expansion:
5

3 |Vnk5 |
2
Vnk5 Vk5 k4 Vk4 n Vnk5 Vk5 k3 Vk3 n
+ Vnn2
2 3 + 2 2 Vnn 4
Enk4 Enk5 Enk3 Enk5 Enk5

|n = nk |k (0) + |n(1) .
and the states to fourth order can be written kD
3.4 Generalization to multi-parameter case 5

For the rst-order perturbation we need to solve the per- 3.4.1 Hamiltonian and force operator
turbed Hamiltonian restricted to the degenerate subspace
D From the dierential geometric point of view, a parame-
terized Hamiltonian is considered as a function dened on
the parameter manifold that maps each particular set of
V |k = k |k + small
(0) (0)
|k D.
(0) parameters (x1 , x2 , ) to an Hermitian operator H(x )
that acts on the Hilbert space. The parameters here can be
simultaneously for all the degenerate eigenstates, where external eld, interaction strength, or driving parameters
k are rst-order corrections to the degenerate energy lev- in the quantum phase transition. Let En(x ) and |n(x )


els, and small is a small vector orthogonal to D. This is be the n-th eigenenergy and eigenstate of H(x ) respec-
equivalent to diagonalizing the matrix tively. In the language of dierential geometry, the states
|n(x ) form a vector bundle over the parameter mani-
fold, on which derivatives of these states can be dened.
The perturbation theory is to answer the following ques-
k |V |l = Vkl
(0) (0)
|k , |l D.
(0) (0)
tion: given En (x0 ) and |n(x0 ) at an unperturbed refer-

This procedure is approximate, since we neglected states ence point x0 , how to estimate the En(x ) and |n(x )

outside the D subspace. The splitting of degenerate ener- at x close to that reference point.
gies k is generally observed. Although the splitting may Without loss of generality, the coordinate system can be
be small compared to the range of energies found in the shifted, such that the reference point x0 = 0 is set to be
system, it is crucial in understanding certain details, such the origin. The following linearly parameterized Hamil-
as spectral lines in Electron Spin Resonance experiments. tonian is frequently used
Higher-order corrections due to other eigenstates can be
found in the same way as for the non-degenerate case
H(x ) = H(0) + x F .
( ) ( ) If the parameters x are considered as generalized coor-
En(0) H0 |n(1) = k (0) |V |n(0) |k (0) .
dinates, then F should be identied as the generalized
kD
force operators related to those coordinates. Dierent
The operator on the left hand side is not singular when indices label the dierent forces along dierent direc-
applied to eigenstates outside D, so we can write tions in the parameter manifold. For example, if x de-
notes the external magnetic eld in the -direction, then
F should be the magnetization in the same direction.
k (0) |V |n(0)
|n(1) = (0) (0)
|k (0) ,
kD E n E k
3.4.2 Perturbation theory as power series expansion

but the eect on the degenerate states is minuscule, pro- The validity of the perturbation theory lies on the adia-
portional to the square of the rst-order correction k . batic assumption, which assumes the eigenenergies and
eigenstates of the Hamiltonian are smooth functions of
Near-degenerate states should also be treated in the above
parameters such that their values in the vicinity region
manner, since the original Hamiltonian won't be larger
can be calculated in power series (like Taylor expansion)
than the perturbation in the near-degenerate subspace.
of the parameters:
An application is found in the nearly free electron model,
where near-degeneracy treated properly gives rise to an
energy gap even for small perturbations. Other eigen-
1
states will only shift the absolute energy of all near- En (x ) = En + x En + x x En +
2!
degenerate states simultaneously.
1
|n(x ) = |n + x | n + x x | n +

2!
3.4 Generalization to multi-parameter Here denotes the derivative with respect to x . When
case applying to the state | n , it should be understood as the
covariant derivative if the vector bundle is equipped with
The generalization of the time-independent perturbation non-vanishing connection. All the terms on the right-
theory to the case where there are multiple small param- hand-side of the series are evaluated at x = 0, e.g. En
eters x = (x1 , x2 , ) in place of can be formulated En(0) and |n |n(0) . This convention will be adopted
more systematically using the language of dierential ge- throughout this subsection, that all functions without the
ometry, which basically denes the derivatives of the parameter dependence explicitly stated are assumed to
quantum states and calculates the perturbative corrections be evaluated at the origin. The power series may con-
by taking derivatives iteratively at the unperturbed point. verge slowly or even not converge when the energy levels
6 3 TIME-INDEPENDENT PERTURBATION THEORY

are close to each other. The adiabatic assumption breaks where denotes the real part function. The rst order
down when there is energy level degeneracy, and hence derivative En is given by the rst HellmannFeynman
the perturbation theory is not applicable in that case. theorem directly. To obtain the second order derivative
En, simply applying the dierential operator to
the result of the rst order derivative n| H|n , which
3.4.3 HellmanFeynman theorems reads
The above power series expansion can be readily eval-
uated if there is a systematic approach to calculate the
En = n| H|n+n| H|n+n| H| n.
derivates to any order. Using the chain rule, the deriva-
tives can be broken down to the single derivative on either Note that for linearly parameterized Hamiltonian, there
the energy or the state. The HellmannFeynman theo- is no second derivative H = 0 on the operator level.
rems are used to calculate these single derivatives. The Resolve the derivative of state by inserting the complete
rst HellmannFeynman theorem gives the derivative of set of basis,
the energy,

En = ( n|mm| H|n + n| H|mm| n) ,
En = n| H|n m

The second HellmannFeynman theorem gives the then all parts can be calculated using the Hellmann
derivative of the state (resolved by the complete basis Feynman theorems. In terms of Lie derivatives,
with m n), n|n = n| n = 0 according to the denition
of the connection for the vector bundle. Therefore, the
case m = n can be excluded from the summation, which
m| H|n m| H|n avoids the singularity of the energy denominator. The
m| n = , m|n = .
En Em Em En same procedure can be carried on for higher order deriva-
tives, from which higher order corrections are obtained.
For the linearly parameterized Hamiltonian, H simply
stands for the generalized force operator F. The same computational scheme is applicable for the cor-
rection of states. The result to the second order is as fol-
The theorems can be simply derived by applying the dif-
lows
ferential operator to both sides of the Schrdinger
equation H|n = En |n, which reads
m| H|n
|n (x ) = |n + |mx
En Em
H|n + H| n = En |n + En | n. m=n

m| H|ll| H|n m| H
Then overlap with the state m| from left and make use + |m
of the Schrdinger equation m|H = m|Em again, (En Em )(En El ) (En
m=n l=n m=n

Both energy derivatives and state derivatives will be in-

m| H|n+Em m| n = En m|n+En m| n. volved in deduction. Whenever a state derivative is en-
countered, resolve it by inserting the complete set of ba-
Given that the eigenstates of the Hamiltonian always form sis, then the Hellmann-Feynman theorem is applicable.
an orthonormal basis m|n = mn , the cases of m = n Because dierentiation can be calculated systematically,
and m n can be discussed separately. The rst case the series expansion approach to the perturbative correc-
will lead to the rst theorem and the second case to the tions can be coded on computers with symbolic process-
second theorem, which can be shown immediately by re- ing software like Mathematica.
arranging the terms. With the dierential rules given by
the HellmannFeynman theorems, the perturbative cor-
rection to the energies and states can be calculated sys- 3.4.5 Eective Hamiltonian
tematically.
Let H(0) be the Hamiltonian completely restricted either
in the low-energy subspace HL or in the high-energy sub-
3.4.4 Correction of energy and state space HH , such that there is no matrix element in H(0)
connecting the low- and the high-energy subspaces, i.e.
To the second order, the energy correction reads m|H(0)|l = 0 if m HL , l HH . Let F = H
be the coupling terms connecting the subspaces. Then
when the high energy degrees of freedoms are integrated
n| H|mm| H|n
En (x ) = n|H|n+n| H|nx +
out, the eective
x xHamiltonian
+ , in the low energy subspace
En reads
Em [6]
m=n
4.1 Method of variation of constants 7

an energy basis |n for the unperturbed system. (We drop

( the (0) superscripts for the eigenstates, because)it is not
e 1 m| H|ll| H|n m| H|ll| H|n
Hmn (x ) = m|H|n+nm m| H|nx + useful to speak of energy
+ levels and eigenstates x for x + .
the
2! E E
perturbed system.)
m l E n E l
lHH

Here m, n HL are restricted in the low energy sub- If the unperturbed system is in eigenstate |j at time t = 0,
space. The above result can be derived by power series its state at subsequent times varies only by a phase (in the
expansion of m|H(x )|n . Schrdinger picture, where state vectors evolve in time
and operators are constant),
In a formal way it is possible to dene an eective Hamil-
tonian that gives exactly the low-lying energy states and
wavefunctions.[7] In practice, some kind of approxima-
|j(t) = eiEj t/ |j .
tion (perturbation theory) is generally required.
Now, introduce a time-dependent perturbing Hamilto-
nian V(t). The Hamiltonian of the perturbed system is
4 Time-dependent perturbation
theory H = H0 + V (t) .

4.1 Method of variation of constants Let |(t) denote the quantum state of the perturbed sys-
tem at time t. It obeys the time-dependent Schrdinger
Time-dependent perturbation theory, developed by Paul equation,
Dirac, studies the eect of a time-dependent perturbation
V(t) applied to a time-independent Hamiltonian H0 .

Since the perturbed Hamiltonian is time-dependent, so H|(t) = i t |(t) .
are its energy levels and eigenstates. Thus, the goals of
time-dependent perturbation theory are slightly dierent The quantum state at each instant can be expressed as a
from time-independent perturbation theory. One is inter- linear combination of the complete eigenbasis of |n :
ested in the following quantities:

The time-dependent expectation value of some ob- |(t) = cn (t)eiEn t/ |n ,
n
servable A, for a given initial state.
where the cn(t)s are to be determined complex functions
The time-dependent amplitudes of those quantum
of t which we will refer to as amplitudes (strictly speak-
states that are energy eigenkets (eigenvectors) in the
ing, they are the amplitudes in the Dirac picture).
unperturbed system.
We have explicitly extracted the exponential phase fac-
The rst quantity is important because it gives rise to tors exp(iEn t/) on the right hand side. This is only
the classical result of an A measurement performed on a matter of convention, and may be done without loss of
a macroscopic number of copies of the perturbed sys- generality. The reason we go to this trouble is that when
tem. For example, we could take A to be the displace- the system starts in the state |j and no perturbation is
ment in the x-direction of the electron in a hydrogen present, the amplitudes have the convenient property that,
atom, in which case the expected value, when multiplied for all t, cj(t) = 1 and cn(t) = 0 if n j.
by an appropriate coecient, gives the time-dependent The square of the absolute amplitude cn(t) is the proba-
dielectric polarization of a hydrogen gas. With an appro- bility that the system is in state n at time t, since
priate choice of perturbation (i.e. an oscillating electric
potential), this allows one to calculate the AC permittivity
of the gas. 2
|cn (t)| = |n|(t)| .
2

The second quantity looks at the time-dependent proba-

Plugging into the Schrdinger equation and using the fact
bility of occupation for each eigenstate. This is partic-
that /t acts by a chain rule, one obtains
ularly useful in laser physics, where one is interested in
the populations of dierent atomic states in a gas when a
time-dependent electric eld is applied. These probabil- ( )
cn
ities are also useful for calculating the quantum broad- i cn (t)V (t) eiEn t/ |n = 0 .
t
ening of spectral lines (see line broadening) and particle n
decay in particle physics and nuclear physics. By resolving the identity in front of V, this can be re-
We will briey examine the method behind Diracs for- duced to a set of coupled dierential equations for the
mulation of time-dependent perturbation theory. Choose amplitudes,
8 4 TIME-DEPENDENT PERTURBATION THEORY

cn i |(t)
= n|V (t)|k ck (t) ei(Ek En )t/ . H(t)|(t) = i
t t
k
has the formal solution
The matrix elements of V play a similar role as in time-
independent perturbation theory, being proportional to [ ]
the rate at which amplitudes are shifted between states. i t
|(t) = T exp dt H(t ) |(t0 ) ,
Note, however, that the direction of the shift is modi- t0
ed by the exponential phase factor. Over times much
longer than the energy dierence Ek En, the phase where T is the time ordering operator,
winds around 0 several times. If the time-dependence
of V is suciently slow, this may cause the state ampli- {
tudes to oscillate. ( E.g., such oscillations are useful for T A(t )A(t ) = A(t1 )A(t2 ) t1 > t2 .
1 2
managing radiative transitions in a laser.) A(t2 )A(t1 ) t2 > t1
Up to this point, we have made no approximations, so Thus, the exponential represents the following Dyson se-
this set of dierential equations is exact. By supplying ries,
appropriate initial values cn(t), we could in principle nd
an exact (i.e., non-perturbative) solution. This is easily
[ t t1 ]
done when there are only two energy levels (n = 1, 2), i t 1
and this solution is useful for modelling systems like the |(t) = 1 dt1 H(t1 ) 2
t0
dt1 dt2 H(t1 )H(t2 ) + . . . |
t0 t0
ammonia molecule.
Note that in the second term, the 1/2! factor exactly can-
However, exact solutions are dicult to nd when there
cels the double contribution due to the time-ordering op-
are many energy levels, and one instead looks for pertur-
erator, etc.
bative solutions. These may be obtained by expressing
the equations in an integral form, Consider the following perturbation problem

i t |(t)
[H + V (t)]|(t) = i ,
cn (t) = cn (0)+ dt n|V (t )|k ck (t ) ei(Ek En0)t / . t
0
k
assuming that the parameter is small and that the prob-
Repeatedly substituting this expression for c back into lem H0 |n = En |n has been solved.
right hand side, yields an iterative solution, Perform the following unitary transformation to the
interaction picture (or Dirac picture),

n + cn + cn +
cn (t) = c(0) (1) (2)

|(t) = e H0 (tt0 ) |I (t) .

i

where, for example, the rst-order term is

Consequently, the Schrdinger equation simplies to

i t

c(1)
n (t) = dt n|V (t )|k ck (0) ei(Ek En )t / . i H0 (tt0 ) |I (t)
V (t)e H0 (tt0 ) |I (t) = i
i
0
e ,
k t
Several further results follow from this, such as Fermis so it is solved through the above Dyson series,
golden rule, which relates the rate of transitions between
quantum states to the density of states at particular en- [
i t i
H0 (t1 t0 ) i H0 (t1 t0 ) 2 t
ergies; or the Dyson series, obtained by applying the it- |I (t) = 1 dt1 e V (t1 )e 2 dt1
erative method to the time evolution operator, which is t0 t0
one of the starting points for the method of Feynman di- as a perturbation series with small .
agrams.
Using the solution
of the unperturbed problem H0 |n =
En |n and n |nn| = 1 (for the sake of simplicity
4.2 Method of Dyson series assume a pure discrete spectrum), yields, to rst order,

Time-dependent perturbations can be reorganized [ t

through the technique of the Dyson series. The | (t) = 1 i dt1 m|V (t1 )|ne (En Em )(t1 t0 ) |mn
i
I
Schrdinger equation m n t0
 9

Thus, the system, initially in the unperturbed state | = the stationary eigenfunctions also given above ( |n() =
|(t0 ) , by dint of the perturbation can go into the state U (0; )|n) .)
| . The corresponding transition probability amplitude The unitary evolution operator is applicable to arbitrary
to rst order is eigenstates of the unperturbed problem and, in this case,
yields a secular series that holds at small times.
t
i
dt1 |V (t1 )|e (E E )(t1 t0 ) ,
i
A =
t0 5 Strong perturbation theory
as detailed in the previous sectionwhile the corre-
sponding transition probability to a continuum is fur- In a similar way as for small perturbations, it is possible
nished by Fermis golden rule. to develop a strong perturbation theory. Let us consider
As an aside, note that time-independent perturbation the- as usual the Schrdinger equation
ory is also organized inside this time-dependent pertur-
bation theory Dyson series. To see this, write the unitary
|(t)
evolution operator, obtained from the above Dyson series, H(t)|(t) = i
as t
and we consider the question if a dual Dyson series ex-
ists that applies
t1 in the limit of a perturbation increasingly
2 t
i t t t large. This question can be answeredi in an armative
dt2 e H0 (t1 t0 ) V (t1 )e H0 (t1 t0 ) e H0[9]
(t2 t0 )
V (t2 )e H0
i i i i i
U (t) = 1 dt1 e 0 1 0 V (t1 )e 0 1 0 2
H (t ) H (t )
dt1
t0 wayt0
[8]
and the
t0 series is the well-known adiabatic series.
This approach is quite general and can be shown in the
and take the perturbation V to be time-independent. following way. Let us consider the perturbation problem
Using the identity resolution

|(t)
[H0 + V (t)]|(t) = i
|nn| = 1 t
n being . Our aim is to nd a solution in the form
with H0 |n = En |n for a pure discrete spectrum, write
1 1
{ | = |0 }
+ |1 + 2 |2 + . . .

t
i
m|V |ne (En Em )(t1but
t0 )
i
U (t) = 1 dt1 a|mn|
direct substitution into the above equation fails to
t0 m n
{ t1 produce useful results. This situation can be adjusted}
2 t i making a rescaling of the time
i variable as = t pro-
dt1 dt2 e (En Em )(t1 t0 ) m|V |nn|V |qe (Eq En )(t2 t0 ) |mq| +
2 t0 t0 m n q
ducing the following meaningful equations

It is evident that, at second order, one must sum on all the

intermediate states. Assume t0 = 0 and the asymptotic |0
V (t)|0 = i
limit of larger times. This means that, at each contri-
bution of the perturbation series, one has to add a mul-
|1
tiplicative factor et in the integrands for arbitrarily V (t)|1 + H0 |0 = i

small. Thus the limit t gives back the nal state of
the system by eliminating all oscillating terms, but keep- ..
.
ing the secular ones. The integrals are thus computable,
that can be solved once we know the solution of the
and, separating the diagonal terms from the others yields
leading order equation. But we know that in this case we
can use the adiabatic approximation. When V (t) does
i i2 n|V |mm|V |n
not depend time one gets the Wigner-Kirkwood series
1 2 on
U (t) = 1 n|V |nt t
that
is often n|V
used |mm|Vmechanics.
in statistical |nt2 + . . .Indeed, in this
n En Em 2 m,n
2
m=n
case we introduce the unitary transformation
m|V |n m|V |nn|V |q
+ |mn| + 2
|mq| + . . .
En Em n
(En Em )(Eq En )
m=n m=n q=n
|(t) = e V (tt0 ) |F (t)
i

where the time secular series yields the eigenvalues of the

perturbed problem specied above, recursively; whereas that denes a free picture as we are trying to eliminate
the remaining time-constant part yields the corrections to the interaction term. Now, in dual way with respect to
10 6 EXAMPLES

the small perturbations, we have to solve the Schrdinger or

equation
( ) 12 2 ( ) 12 3 1 3 2
(1)
E0 = = =
|F (t) 2
4 2 4 m2 2
e V (tt0 ) H0 e V (tt0 ) |F (t) = i
i i

t
and we see that the expansion parameter appears only 6.2 Example of rst and second order per-
into the exponential and so, the corresponding Dyson se- turbation theory quantum pendulum
ries, a dual Dyson series, is meaningful at large s and
is Consider the quantum mathematical pendulum with the
Hamiltonian
[ t t1
i t 1
dt1 e V (t1 t0 ) H0 e V (t1 t0 ) 2 V (t1 t0 )
H0 e V (t1 t0 ) e V (t2 t0 ) H0 e V (t2
i i i i i i
|F (t) = 1 dt12 dt2 2e
t0
H = 0
t t 0 cos
2ma2 2
After the rescaling in time = t we can see that
this is indeed a series in 1/ justifying in this way the with the potential energy cos taken as the perturba-
name of dual Dyson series. The reason is that we tion i.e.
have obtained this series simply interchanging H 0 and
V and we can go from one to another applying this ex-
change. This is called duality principle in perturba- V = cos
tion theory. The choice H0 = p2 /2m yields, as already
said, a Wigner-Kirkwood series that is a gradient expan- The unperturbed normalized quantum wave functions are
sion. The Wigner-Kirkwood series is a semiclassical se- those of the rigid rotor and are given by
ries with eigenvalues given exactly as for WKB approxi-
mation.[10]
ein
n () =
2
6 Examples and the energies

6.1 Example of rst order perturbation

theory ground state energy of the En(0) = n 2
2 2

2ma
quartic oscillator
The rst order energy correction to the rotor due to the
Let us consider the quantum harmonic oscillator with the potential energy is
quartic potential perturbation and the Hamiltonian

1 in 1
En =
(1)
e cos ein
= cos = 0
2 2 m 2 x2 2 2
H= + + x 4
2m x2 2 Using the formula for the second order correction one
The ground state of the harmonic oscillator is gets

 2
( ) 14 ma2  eik cos ein 
x2 /2
0 = e En(2) =
2 2 2 n2 k 2
k
( = m/ ) and the energy of unperturbed ground or
state is

ma2 |(n,1k + n,1k )|

2
(0) En(2) =
2 .
1
E0 = 22 n2 k 2
k

Using the rst order correction formula we get or

( ) 12 ( ) 12 2 2
( )
(1) x2 /2 4 x2 /2
ma
(2) x2 1 1 ma2 1
E0 = e x e dx = E e= dx + =
2 n
2 2 2n 1 2n 1 4n 1
2 2
 11

7 References
[1] Aoyama, Tatsumi; Hayakawa, Masashi; Kinoshita, To-
ichiro; Nio, Makiko (2012). Tenth-order QED lepton
anomalous magnetic moment: Eighth-order vertices con-
taining a second-order vacuum polarization. Physical
Review D. American Physical Society. 85 (3): 033007.
arXiv:1110.2826 . Bibcode:2012PhRvD..85c3007A.
doi:10.1103/PhysRevD.85.033007.

[2] Schrdinger, E. (1926). Quantisierung als Eigen-

wertproblem [Quantication of the eigen value
problem]. Annalen der Physik (in German). 80
(13): 437490. Bibcode:1926AnP...385..437S.
doi:10.1002/andp.19263851302.

[3] Rayleigh, J. W. S. (1894). Theory of Sound. I (2nd ed.).

London: Macmillan. pp. 115118. ISBN 1-152-06023-
6.

[4] Sakurai, J.J., and Napolitano, J. (1964,2011). Modern

quantum mechanics (2nd ed.), Addison Wesley ISBN 978-
0-8053-8291-4 . Chapter 5

[5] Landau, L. D.; Lifschitz, E. M. Quantum Mechanics: Non-

relativistic Theory (3rd ed.). ISBN 0-08-019012-X.

[6] Bir, Gennadi Levikovich; Pikus, Grigori Ezekielevich

(1974). Chapter 15: Perturbation theory for the degen-
erate case. Symmetry and Strain-induced Eects in Semi-
conductors. ISBN 978-0-470-07321-6.

[7] Soliverez, Carlos E. (1981). General The-

ory of Eective Hamiltonians. Physical Re-
view A. 24: 49. Bibcode:1981PhRvA..24....4S.
doi:10.1103/PhysRevA.24.4 via Academia.Edu.

[8] Frasca, M. (1998). Duality in Perturbation The-

ory and the Quantum Adiabatic Approximation.
Physical Review A. 58 (5): 3439. arXiv:hep-
th/9801069 . Bibcode:1998PhRvA..58.3439F.
doi:10.1103/PhysRevA.58.3439.

[9] Mostafazadeh, A. (1997). Quantum adia-

batic approximation and the geometric phase,.
Physical Review A. 55 (3): 1653. arXiv:hep-
th/9606053 . Bibcode:1997PhRvA..55.1653M.
doi:10.1103/PhysRevA.55.1653.

[10] Frasca, Marco (2007). A strongly perturbed quan-

tum system is a semiclassical system. Proceedings
of the Royal Society A: Mathematical, Physical and
Engineering Sciences. 463 (2085): 2195. arXiv:hep-
th/0603182 . Bibcode:2007RSPSA.463.2195F.
doi:10.1098/rspa.2007.1879.
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