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3 Hydrogen Atom DPT Tutorial55

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23 views58 pages

3 Hydrogen Atom DPT Tutorial55

Ob 6gur

Uploaded by

HARDIK GARG

We take content rights seriously. If you suspect this is your content, claim it here.

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Download as PDF, TXT or read online on Scribd

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Name

Finding Splitting in the Hydrogen Atom Energy Spectrum due

to an External Magnetic Field (Zeeman Effect)-PART II
The focus in degenerate perturbation theory is on ensuring that Ĥ 0 is diagonal in each degenerate subspace
of Ĥ 0 . The degeneracy in Ĥ 0 is 2n2 fold for each n. Our focus is always on a fixed n. The radial basis states
are always Rnl (r), which are solutions to the radial part of the time-independent Schrödinger equation for Ĥ 0 .
We will learn how to determine a “good” angular basis.

1 Definition
For a given unperturbed Hamiltonian Ĥ 0 and perturbation Ĥ 0 , a “good” basis consists of a complete set of
eigenstates of Ĥ 0 that diagonalizes Ĥ 0 in each degenerate subspace of Ĥ 0 (Ĥ 0 remains diagonal everywhere
since the basis states are eigenstates of Ĥ 0 ).

• Once you have a “good” basis for a given Ĥ 0 and Ĥ 0 , you can use the same expressions that you use in
non-degenerate perturbation theory for perturbative corrections.

2 Notes for this tutorial:

* If you are not familiar with the steps to determine a “good” basis for finding corrections to the unperturbed
energies when the energy spectrum has degeneracy, please work through the pretest, tutorial and posttest
for Basics of Degenerate Perturbation Theory before working on this tutorial.

* A Hermitian operator Q̂ has the property Qij = (Qji )∗ . Here ∗ denotes the complex conjugate.

* For the matrix representation of a Hermitian operator Q̂ in a given basis, we will use “=” or “is equal
.
to” instead of “=” or “is represented by” as in the notation below
   
Q11 Q12 Q13 Q11 Q12 Q13
.
Q̂ =  Q21 Q22 Q23  is equivalent to Q̂ =  Q21 Q22 Q23  .
Q31 Q32 Q33 Q31 Q32 Q33

* In this tutorial, “degeneracy” indicates degeneracy in the unperturbed energy eigenvalue spectrum, i.e.,
the fact that more than one distinct energy eigenstate can have the same energy eigenvalue. For example,
if
Ĥ 0 |ψa i = Ea |ψa i and Ĥ 0 |ψb i = Ea |ψb i,
|ψa i and |ψb i are degenerate eigenstates of the Hamiltonian Ĥ 0 since they correspond to the same energy
Ea .

* We will only consider the bound states of the hydrogen atom.

* The unperturbed bound state energies En are given by En = − 13.6eV

n2
, n = 1, 2, 3, . . ..

* For any basis we choose, the radial parts of the wavefunctions Rnl (for given quantum
numbers n and l) will always be chosen to be the radial parts of a complete set of eigenstates
of Ĥ 0 . In other words, our focus will be on the choice of the angular part of the wavefunction
in order to find a “good” basis for degenerate perturbation theory for the given Ĥ 0 and Ĥ 0
for the hydrogen atom.

1
* We will restrict our focus to a finite subspace of the infinite dimensional Hilbert space.

– As an example of a degenerate subspace of the unperturbed Hamiltonian Ĥ 0 , only the subspace with
the principal quantum number n = 2 will be considered.
– The results can be generalized to any quantum number n.

* The external magnetic field will be chosen to be a uniform, time independent field along the ẑ direction
~ = Bext ẑ.
given by B

* We will account for the coupling of the external magnetic field with both the orbital and spin angular
momentum.

* We will use the following notations interchangeably to write states in the uncoupled representation (in
which basis states are eigenstates of L̂2 , Ŝ 2 , L̂Z , and ŜZ ) with a given set of quantum numbers (notation
for quantum numbers is standard):

– |n l s ml ms i
– |l, ml i|s, ms i (if n is fixed)
– |l, ml , ms i (if n and s are fixed)

* J~ = L
~ +S
~

* We will use the following notations interchangeably to write states in the coupled representation (in which
basis vectors are eigenstates of L̂2 , Ŝ 2 , Jˆ2 , and JˆZ ) with a given set of quantum numbers (notation for
quantum numbers is standard):

– |n l s j mj i
– |l, s, j, mj i (if n is fixed)
– |l, j, mj i (if n and s are fixed)
1
* In both Part I and Part II of this tutorial, we will consider the case in which s = 2 so this quantum
number may be suppressed in writing a state (e.g., |l ml ms i or |l j mj i).

3 Physical Constants
Below is a list of physical constants used in this tutorial.
Planck’s constant: h̄ = 1.05 × 10−34 J s

Mass of the electron: m = 9.11 × 10−31 kg

Charge of an electron (magnitude): e = 1.60 × 10−19 C

Speed of light: c = 2.99 × 108 m/s

Permittivity of space: 0 = 8.85 × 10−12 C2 /J m

4π0 h̄2
Bohr radius: a = me2
= 0.529 × 10−10 m

Bohr magneton: µB = eh̄

2m = 5.79 × 10−5 eV/T

e2
Fine structure constant: α = 4π0 h̄c ≈ 1
137 = 7.30 × 10−3

2
NOTE : The following equations may be helpful.

En1 = hψn0 |Ĥ 0 |ψn0 i

X hψ 0 |Ĥ 0 |ψ 0 i
m n
|ψn1 i = 0
|ψm i
(En0 − Em 0)
m6=n

Ŝ 2 |s ms i = h̄2 s(s + 1)|s ms i Ŝz |s ms i = h̄ms |s ms i

p
Ŝ± |s ms i = h̄ s(s + 1) − ms (ms ± 1))|s ms ± 1i

L̂2 |l ml i = h̄2 l(l + 1)|l ml i L̂z |l ml i = h̄ml |l ml i

p
L̂± |l ml i = h̄ l(l + 1) − ml (ml ± 1))|l ml ± 1i

J~ = L
~ +S
~

Jˆ2 |l, s, j, mj i = h̄2 j(j + 1)|l, s, j, mj i Jˆz |l, s, j mj i = h̄mj |l, s, j, mj i

Ŝ 2 |l, s, j, mj i = h̄2 s(s + 1)|l, s, j, mj i L̂2 |l, s, j mj i = h̄2 l(l + 1)|l, s, j, mj i

~ = 1 (Jˆ2 − Ŝ 2 − L̂2 ) = 1 (L̂+ Ŝ− + L̂− Ŝ+ ) + L̂z Ŝz

~ ·S
L
2 2

3
4 Objectives:
Upon completion of this tutorial, you should be able to do the following for the hydrogen atom:

1. Identify the unperturbed Hamiltonian Ĥ 0 and the perturbing Hamiltonian Ĥ 0 .

2. Identify the degeneracy in the unperturbed Hamiltonian Ĥ 0 in each degenerate subspace corresponding
to a principal quantum number n.

3. Determine a “good” basis for finding the corrections to the unperturbed energies of the hydrogen atom
for only the fine structure perturbation Ĥf0 s .

4. Find the first order corrections to energies due to the fine structure perturbation Ĥf0 s .

5. Determine a “good” basis for finding the corrections to the unperturbed energies of the hydrogen atom
due to the Zeeman effect (including in intermediate, strong, and weak magnetic field).

6. Find the first order corrections to energies in the intermediate field Zeeman effect.

7. Find the first order corrections to energies in the strong field Zeeman effect.

8. Find the first order corrections to energies in the weak field Zeeman effect.

5 The Hydrogen Atom Placed in an External Magnetic Field

The Hamiltonian of the hydrogen atom placed in an external magnetic field is

Ĥ = Ĥ 0 + Ĥr0 + ĤSO
0
+ ĤZ0 = Ĥ 0 + Ĥf0 s + ĤZ0 (1)

in which
2
p̂ e2 1
• Ĥ 0 = 2m

− 4π0 r accounts only for the interaction of the electron with the nucleus via Coulomb
attraction
4
• Ĥr0 = − 8mp̂3 c2 is the relativistic correction term
0 e2 1 ~ ~ is the spin-orbit interaction term
• ĤSO = 8π0 m2 c2 r3 L ·S

and combining the relativistic and spin-orbit terms

• Ĥf0 s = ĤSO
0 + Ĥr0 is the fine structure term
µB Bext ~ ext = Bext ẑ.
• ĤZ0 = h̄ (L̂z + 2Ŝz ) is the Zeeman term, in which B

4
6 Perturbation Theory
• In order to find the first order corrections to the energies due to a perturbation Ĥ 0 , we must first find a
“good” basis for the given Ĥ 0 and Ĥ 0 .

• A “good” basis is defined as one which satisfies the following two conditions:

1. The entire unperturbed Hamiltonian Ĥ 0 is diagonal (i.e., basis states are eigenstates of Ĥ 0 ).
– We know from Part I of this tutorial that the unperturbed Hamiltonian matrix Ĥ 0 is diagonal
if the coupled or uncoupled representation or any arbitrary complete orthonormal basis found
with linear combinations of a complete set of the coupled or uncoupled states with the same
principal quantum number n is chosen as the angular basis (as a consequence of the spherical
symmetry of Ĥ 0 and the unperturbed energy only depending on n as En = − 13.6
n2
eV
).
2. The perturbing Hamiltonian Ĥ 0 is diagonal in each degenerate subspace of Ĥ 0 .
– We always choose Rnl as the radial part of the basis and focus on the angular basis for deter-
mining a “good” basis for a given Ĥ 0 and Ĥ 0 .
– We shall consider several types of perturbing Hamiltonian, Ĥ 0 , and determine whether the cou-
pled representation, the uncoupled representation, some special orthonormal basis constructed
with linear combinations of the coupled or the uncoupled states, or any arbitrary complete or-
thonormal basis constructed with linear combinations of the coupled or the uncoupled states
with the same principal quantum number n and the same l diagonalizes Ĥ 0 in each degenerate
subspace of Ĥ 0 .

• In Part I, we found:

– Ĥ 0 (spherically symmetric with energy only depending on n as En = − 13.6n2

eV
) is diagonal if the
coupled representation, the uncoupled representation, or any arbitrarycomplete orthonormal basis
constructed with linear combinations of a complete set of states in the coupled or the uncoupled
representation (with the same n) is chosen as the angular basis.
– Ĥr0 (spherically symmetric with energy depending on both n and l) is diagonal in each degenerate
subspace of Ĥ 0 if the coupled representation, the uncoupled representation, or any arbitrary complete
orthonormal basis constructed with linear combinations of states with the same n and l in the coupled
or the uncoupled representation is chosen as the angular basis.
0
– ĤSO is diagonal in each degenerate subspace of Ĥ 0 if the coupled representation is chosen as the
angular basis.
– ĤZ0 is diagonal if the uncoupled representation is chosen as the angular basis.

5
6.1 The Hydrogen Atom in an External Magnetic Field
• In order to find the corrections to the unperturbed energies in the presence of an external magnetic field,
we shall consider the following two terms in the Hamiltonian perturbatively:

Ĥ 0 = Ĥf0 s + ĤZ0 (2)

in which Ĥf0 s is the fine structure correction term and ĤZ0 is the Zeeman term incorporating the effect of
the external magnetic field.

• The perturbative corrections due to these terms are small compared to the unperturbed energies due to
Ĥ 0 , but both terms are important in terms of determining splittings in the energy spectrum so that they
should both be considered simultaneously.

• Let’s first consider the fine structure. Here is the order in which we shall proceed:

I. Determining a “good” angular basis and corrections to the energies for ONLY the fine structure
perturbation Ĥf0 s .

0 , in which Ĥ 0 is
– The fine structure correction Ĥf0 s is made up of two mechanisms: Ĥf0 s = Ĥr0 + ĤSO r
the relativistic correction term and ĤSO0 is the spin-orbit interaction term (due to the coupling of
the orbital and spin angular momenta of the electron).

II. Determining a “good” angular basis and corrections to the energies for ONLY the Zeeman per-
turbation ĤZ0 .

– The Zeeman effect in the hydrogen atom (or any atom) is the splitting of the energy spectrum as a
result of placing the atom in an external magnetic field.

III. Determining a “good” angular basis and corrections to the energies for BOTH the fine structure
and Zeeman perturbations combined: Ĥ 0 = Ĥf0 s + ĤZ0 .

– In this tutorial we will learn about three cases with Ĥ 0 = Ĥf0 s + ĤZ0 :
∗ CASE 1: The Intermediate Field Zeeman Effect
· The intermediate field Zeeman effect describes a situation when the first-order corrections
to the energies due to the spin-orbit coupling term Ĥf0 s and the Zeeman term ĤZ0 in Ĥ 0 are
comparable to one another. (We will use the notations EZ0 ≈ Ef0 s to denote the intermediate
field Zeeman effect).
– along with two limiting cases:
∗ CASE 2: The Strong Field Zeeman Effect (EZ0 Ef0 s )
· The strong field Zeeman effect describes a situation when the first-order corrections to the
energies due to the Zeeman term is stronger than the first-order corrections to the energies
due to the spin-orbit coupling term in Ĥ 0 . (We will use the notation EZ0 Ef0 s to denote
the strong field Zeeman effect).
∗ CASE 3: The Weak Field Zeeman Effect (Ef0 s EZ0 )
· The weak field Zeeman effect describes a situation when the first-order corrections to the
energies due to the spin-orbit coupling term is stronger than the first-order corrections to
the energies due to the Zeeman term in Ĥ 0 . (We will use the notation Ef0 s EZ0 to denote
the weak field Zeeman effect)

6
I. Determining a “GOOD” Angular Basis and Corrections to the Energies
for ONLY the Fine Structure Perturbation Ĥf0 s .

As noted, the fine structure perturbation is comprised of two mechanisms: the relativistic correction Ĥr0 and
0 :
the spin-orbit interaction ĤSO
Ĥf0 s = Ĥr0 + ĤSO
0
. (3)
We shall discuss each separately and then find the first order corrections to the energies of the hydrogen atom
due to the combined effect of the relativistic correction and the spin-orbit interaction.

Relativistic Correction

6.2 Finding a “GOOD” Basis for the Relativistic Correction Term as a Perturbation for the Hydrogen Atom

2
e2 1
A perturbation Ĥr0 acts on a hydrogen atom with the unperturbed Hamiltonian Ĥ 0 = − 2m
h̄
∇2 − 4π0 r such
that the relativistic correction term in the Hamiltonian is
p̂4
Ĥr0 = − . (4)
8m3 c2

1. For the perturbation Ĥr0 , will a “good” angular basis for finding the corrections to the energies be the
coupled representation, the uncoupled representation, or any arbitrary complete orthonormal basis con-
structed with linear combinations of the coupled or uncoupled states with the same principal quantum
number n and the same l? Explain.

Consider the following conversation regarding finding a “good” basis for the relativistic term Ĥr0 as a pertur-
bation on Ĥ 0 for the hydrogen atom.
Student 1: We found that for a fixed n the spherically symmetric unperturbed Hamiltonian Ĥ 0 is diag-
onal in the coupled or the uncoupled representation, as well as in any arbitrary complete orthonormal basis
constructed with linear combinations of states in the coupled representation or the uncoupled representation.
Since the relativistic correction Ĥr0 is also spherically symmetric, Ĥr0 will also be diagonal in the coupled or the
uncoupled representation, as well as in any arbitrary complete orthonormal basis constructed with linear com-
binations of basis states with the same n and l in the coupled representation or the uncoupled representation.
p̂2 e2 1
Student 2: I agree. Ĥ 0 = 2m − 4π ( ) and Ĥr0 is proportional to p̂4 . Both terms are spherically symmetric
0 r
~ˆ = 0 and [Ĥr0 , L]
because [Ĥ 0 , L] ~ˆ = 0. However, the eigenvalues of Ĥ 0 only depend on n while the eigenvalues
of Ĥ 0 depend on both n and l. Thus, Ĥr0 will also be diagonal in both the coupled and the uncoupled repre-
sentation, as well as any arbitrary complete orthonormal basis constructed with linear combinations of states
in the coupled representation or the uncoupled representation.
Student 3: I disagree with both Student 1 and Student 2. The fact that Ĥr0 is spherically symmetric is not
enough information to determine whether the coupled or uncoupled representation or both will form a “good”
angular basis.
Student 4: I agree with Student 1 and Student 2. For finding the corrections to the energies due to the
perturbation Ĥr0 , a “good” angular basis can be chosen to be the coupled representation, the uncoupled rep-
resentation, or any arbitrary complete orthonormal basis found with linear combinations of the coupled or
uncoupled states with the same principal quantum number n and the same l.

Explain why you agree or disagree with each student.

7
The relativistic correction term Ĥr0 is spherically symmetric and its energy eigenvalues depend on the quantum
numbers n and l, and therefore the coupled representation, the uncoupled representation, or any arbitrary
complete orthonormal basis constructed with linear combinations of states with a fixed n and l in the coupled
or the uncoupled representation will form a “good” basis. For example, using the same reasoning as for the
unperturbed Hamiltonian Ĥ 0 and the example when Ĥ 0 was proportional to δ(r) in Part I of this tutorial,
for a given n and l, Ĥr0 will be a diagonal in each degenerate subspace of Ĥ 0 because the angular part of the
matrix elements of Ĥr0 will involve hl, j, mj |l0 , j 0 , m0j i = δl,l0 δj,j 0 δmj ,m0j if we choose the coupled representation
or hl, ml , ms |l0 , m0l , m0s i = δl,l0 δml ,m0l δms ,m0s if we choose the uncoupled representation. The off-diagonal matrix
elements will be zero due to the Kronecker deltas in either case.

Check your answers to question 1.

1. The coupled representation, the uncoupled representation, or any arbitrary complete orthonormal basis
constructed with linear combinations of states with the same n and l in the coupled or the uncoupled
representation with the same principal quantum number n and the same l will form a “good” angular
basis for finding the corrections to the energies of the hydrogen atom due to the spherically symmetric
4
relativistic correction term Ĥr0 = − 8mp̂3 c2 .

If your answer to question 1 does not match with the checkpoint, go back and reconcile any differences.

6.3 First Order Corrections to the Energy Spectrum of the Hydrogen Atom Due to the Relativistic Correction
Term Using Perturbation Theory
Now that we have determined that the coupled representation, the uncoupled representation, or any arbitrary
complete orthonormal basis constructed with linear combinations of states in the coupled or the uncoupled
representation form a “good” angular basis for Ĥr0 as the perturbation, we can determine the corrections to the
energies.

• Let {|ψn i} represent a “good” basis set in which the quantum numbers to describe the angular part of
the {|ψn i} have been suppressed (those quantum numbers will depend, e.g., on whether we choose the
coupled or uncoupled representation for the angular part).

• If {|ψn i} forms a “good” basis for Ĥr0 as a perturbation on the unperturbed Hamiltonian Ĥ 0 , then the first
order correction to the energy due to Ĥr0 is given by (using the fact that p̂2 is Hermitian, i.e., (p̂2 )† = p̂2 )
p̂4 1
Er0 = hψn |Ĥr0 |ψn i = hψn | − |ψn i = − 3 2 hp̂2 ψn |p̂2 ψn i. (5)
8m3 c2 8m c

Consider the following statement regarding evaluating p̂2 |ψn i.

Student 1: We evaluate p̂2 |ψn i by considering the Time-Independent Schrödinger Equation or TISE for the
p̂2
unperturbed Hamiltonian Ĥ 0 |ψn i = En |ψn i. Using the TISE [ 2m + V (r)]|ψn i = En |ψn i, rearranging and
solving for p̂2 |ψn i gives p̂2 |ψn i = 2m[En − V (r)]|ψn i which is helpful in evaluating Er0 in equation (5). Using
hp̂2 ψn |p̂2 ψn i = (2m)2 hψn |[En − V (r)]2 |ψn i, in which V (r) for the hydrogen atom is proportional to 1r , we can
find the first order corrections to the energies due to Ĥr0 in Eq. (5).
Do you agree with Student 1’s approach? Explain your reasoning.

8
Student 1’s method is helpful in determining p̂2 |ψn i. The first order correction to the energy due to Ĥr0 in the
“good” basis {|ψn i} is given by
1 1 1
Er0 = − 3 2
hp̂2 ψn |p̂2 ψn i = − 3 2 hψn |[2m(En −V (r))]2 |ψn i = − hψn |En2 −2En V (r)+(V (r))2 |ψn i. (6)
8m c 8m c 2mc2
2
1 e
For the Coulomb potential energy V (r) = − , the first order correction to the energy becomes
4π0 r
" 2 2 #
1 e 2 1 e 1
Er0 = − 2
hψn | En2 + 2En + |ψn i. (7)
2mc 4π0 r 4π0 r2

It can be shown that using the radial part of the wavefunction Rnl (for a given n and l) for the unperturbed
Hamiltonian Ĥ 0 for the hydrogen atom yields

1 1 1 1
= 2 and 2
=
r n a r (l + 1/2)n3 a2

with Bohr radius

4π0 h̄2
a= .
me2
The first order correction to the nth energy state En due to the relativistic correction is

En2

0 4n
Er = − −3 . (8)
2mc2 l + 1/2

In one to two sentences, summarize what you have learned about the “good” angular basis states for finding
the first order corrections to the energy spectrum of the hydrogen atom due to the relativistic correction Ĥr0
(pertaining to whether the coupled representation, the uncoupled representation, or any arbitrary complete
orthonormal basis found with linear combinations of states with the same principal quantum number n and the
same l in the coupled or uncoupled representation form a “good” angular basis or all of them form a “good”
angular basis).

9
Summary: Finding a “GOOD” Angular Basis for the Relativistic Correction

• The perturbation matrix due to the relativistic correction Ĥr0 is a diagonal matrix in the degenerate subspace of Ĥ 0 in both the coupled and
the uncoupled representation, or in any arbitrary complete orthonormal basis constructed with linear combinations of the coupled or uncoupled
states with the same principal quantum number n and the same l.

• The coupled representation, the uncoupled representation, or any arbitrary complete orthonormal basis constructed with linear combinations
of the coupled or uncoupled states with the same principal quantum number n and the same l form a “good” basis for finding corrections to
the energies.
10

Hamiltonian Uncoupled Is Uncoupled Coupled Is Coupled Is Any Arbitrary Complete Orthonormal Energy
Representation Representation Representation Representation Basis Constructed with Linear Combinations
(for a fixed n) a “Good” Basis? (for a fixed n) a “Good” Basis? of a Complete Set of States with the
Same n and l in the Coupled or Uncoupled
Representation a “Good” Basis?

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

2
h i
En
Ĥr0 Diagonal Yes Diagonal Yes Yes Er0 = − 2mc 2
4n
l+1/2 −3
Spin-orbit Interaction

6.4 Finding a “GOOD” Angular Basis for the Spin-orbit Interaction Correction to the Energy Spectrum of
the Hydrogen Atom in Perturbation Theory

2
0 h̄ e2 1
A perturbation ĤSO acts on a hydrogen atom with the unperturbed Hamiltonian Ĥ 0 = − 2m ∇2 − 4π0 r such
that the spin-orbit interaction term in the Hamiltonian is

0 e2 1 ~ ~
ĤSO = L · S. (9)
8π0 m2 c2 r3

0
2. In each degenerate subspace of Ĥ 0 , the off-diagonal matrix elements of ĤSO should be zero in a “good”
basis. Does the coupled or the uncoupled representation, or any arbitrary complete orthonormal basis
found with linear combinations of the coupled or uncoupled states with the same principal quantum num-
ber n form a “good” angular basis for finding the corrections to the energies? Explain.

Consider the following conversation about finding a “good” angular basis for the hydrogen atom due to the
spin-orbit interaction term as the perturbation.
Student 1: The spin-orbit interaction term is proportional to L ~ · S.
~ Does the coupled or uncoupled represen-
tation, or any arbitrary complete orthonormal basis found with their linear combination form a “good” angular
basis for finding the corrections to the energies?
Student 2: Since L ~ ·S
~ = L̂x Ŝx + L̂y Ŝy + L̂z Ŝz , the uncoupled representation must be a “good” basis because
the basis states in the uncoupled representation are eigenstates of both Ŝz and L̂z .
Student 3: I disagree with Student 2. S ~ ·L ~ is diagonal in the coupled representation because J 2 =
~ + S)
(L ~ · (L ~ + S)
~ = L̂2 + Ŝ 2 + 2L ~ ·S ~ which implies L ~ ·S
~ = 1 (Jˆ2 − Ŝ 2 − L̂2 ). The basis states in the
2
coupled representation are eigenstates of Jˆ2 , Ŝ 2 , and L̂2 and hence eigenstates of L ~ · S.
~
0
Student 4 I agree with Student 3. ĤSO is diagonal in each degenerate subspace of Ĥ 0 when the coupled
representation is chosen as the basis, but not when the uncoupled representation is chosen as the basis. The
coupled representation forms a “good” basis for the given Ĥ 0 and ĤSO 0 .

Do you agree with Student 2 or Student 3? Explain.

~ ·L
(If you need further help with why S ~ is diagonal in the coupled representation, see Part I of this tutorial.)

11
** Check your answer to question 2. **

2. The coupled representation forms a “good” angular basis for finding the corrections to the energies of
0 .
the hydrogen atom due to the spin-orbit interaction term ĤSO

If your answer to question 2 does not match with the checkpoint, go back and reconcile any differences.

6.5 First Order Corrections to the Energy Spectrum of the Hydrogen Atom in Perturbation Theory Due to
the Spin-orbit Interaction
Student 3 is correct in the preceding conversation in stating that the coupled representation will form a “good”
angular basis for finding the correction to the energy due to the spin-orbit interaction as a perturbation. The
first order corrections to the energies due to the spin-orbit interaction in a “good” basis are given by
2
0 0 e 1 1~ ~
ESO = hn l s j mj |ĤSO |n l s j mj i = 2 2
hn l s j mj | 3 L · S|n l s j mj i
8π0 m c r

0 1~ ~
ESO = Ahn l s j mj | L · S|n l s j mj i (10)
r3

e2 1
where A = 8π0 m 2 c2
.

Separating the radial (Rnl (r)) and angular parts of eigenstates {|ψi} of Ĥ 0 in the coupled representation, the
angular part is
* +
D E ˆ2 − L̂2 − Ŝ 2
J h̄2
l s j mj L~ ·S
~ l s j mj = l s j mj l s j mj = [j(j + 1) − l(l + 1) − s(s + 1)] (11)
2 2

and the radial part is

1 1
nl 3 nl = . (12)
r l(l + 1)(l + 1/2)n3 a3
Thus, combining equations (10), (11), and (12), the first order correction to the energy due to the spin-orbit
interaction is
En2 n(j(j + 1) − l(l + 1) − 3/4)

0
ESO = . (13)
mc2 l(l + 1)(l + 1/2)

In one to two sentences, summarize what you have learned about the “good” states for finding the first order
0
corrections to the energy spectrum of the hydrogen atom due to the spin-orbit interaction ĤSO (pertaining to
whether the coupled representation, the uncoupled representation, or any arbitrary complete orthonormal basis
found with linear combinations of states with a fixed principal quantum number n in the coupled or uncoupled
representation form a “good” basis).

12
Summary: Finding a “GOOD” Angular Basis for the Spin-orbit Interaction Term ĤSO 0

h i
0
• ĤSO ~ · S)
= A r13 (L ~ = A 13 1 (Jˆ2 − L̂2 − Ŝ 2 ) is diagonal in the each degenerate subspace of Ĥ 0 in the coupled representation.
r 2

– The basis states in the coupled representation are eigenstates of Jˆ2 , L̂2 and Ŝ 2 and hence ĤSO
0 is diagonal in each degenerate subspace of
0
Ĥ if the coupled representation is chosen as the angular basis.
0 .
• The coupled representation forms a “good” angular basis for finding the corrections to the energies of the hydrogen atom due to ĤSO

Hamiltonian Uncoupled Is the Uncoupled Coupled Is the Coupled Is Any Arbitrary Complete Orthonormal Energy
Representation Representation Representation Representation Basis Constructed with Linear Combinations
(for a fixed n) a “Good” Basis? (for a fixed n) a “Good” Basis? of a Complete Set of States with the
Same n and l in the Coupled or Uncoupled
Representation a “Good” Basis?

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

n2
13

2
h i
En
Ĥr0 Diagonal Yes Diagonal Yes Yes Er0 = − 2mc 2
4n
l+1/2 −3

2
h i
0 0 En n(j(j+1)−l(l+1−3/4))
ĤSO Not Diagonal No Diagonal Yes No ESO = mc2 l(l+1)(l+1/2)
Fine Structure Correction

6.6 Finding a “Good” Angular Basis for the Fine Structure Correction Term to the Energy Spectrum of the
Hydrogen Atom in Perturbation Theory
Consider the following conversation regarding finding a “good” angular basis for fine structure term Ĥf0 s =
Ĥr0 + ĤSO
0 as a perturbation on the unperturbed Hamiltonian Ĥ 0 .
Student 1: The fine structure term Ĥf0 s is made up of two mechanisms: ĤSO 0 and Ĥr0 . The “good” angular
basis is one in which both ĤSO0 and Ĥr0 are diagonal in each degenerate subspace of Ĥ 0 .
Student 2: I agree. In the preceding table, the coupled representation is a “good” angular basis for both the
relativistic correction term Ĥr0 and the spin-orbit interaction term ĤSO
0 , because Ĥ 0 and Ĥ 0
r SO are both diagonal
0
in each degenerate subspace of Ĥ in the coupled representation. Therefore, the coupled representation forms a
“good” angular basis for finding the corrections to the energies due to the fine structure term Ĥf0 s = Ĥr0 + ĤSO
0 .

Explain why you agree or disagree with each student.

6.7 First Order Corrections to the Energy Spectrum of the Hydrogen Atom in Perturbation Theory Due to
the Fine Structure
Combining the first order corrections to the energies for the hydrogen atom due to the relativistic correction
term in equation (8) and spin-orbit interaction term from equation (13) gives the first order correction to the
energies due to the fine structure correction term in the hydrogen atom.

En2

0 4n
Ef s = − −3 (14)
2mc2 (j + 1/2)

3. How many distinct energies does the n = 2 state split into? Explain. [Hint: How many possible values of
j are there for the n = 2 subspace?]

14
** Check your answer to question 3. **

3. For n = 2, there are two possible values of j, j = { 12 , 32 }. The energies split into two distinct levels.

l s j Ef0 s Number of States

1 1 5E22
0 − 2
2 2 2mc2

1 1 5E22
1 − 2
2 2 2mc2

1 3 E22
1 − 4
2 2 2mc2

If your answers to question 3 do not match with the checkpoint, go back and reconcile any differences.

In one to two sentences, summarize what you have learned about the “good” angular basis states for finding
the first order corrections to the energy spectrum of the hydrogen atom due to the fine structure term Ĥf0 s
(pertaining to whether the coupled representation, the uncoupled representation, or any arbitrary complete
orthonormal basis found with linear combinations of states with a fixed principal quantum number n in the
coupled or uncoupled representation form a “good” angular basis).

15
Summary: Finding a “GOOD” Angular Basis for the Fine Structure

• For the entire fine structure perturbation Ĥ 0 = Ĥr0 + ĤSO

0 , the coupled representation forms a “good” angular basis because Ĥ 0 is diagonal in
fs
each degenerate subspace of Ĥ 0 in the coupled representation.

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

2
h i
En
Ĥr0 Diagonal Yes Diagonal Yes Yes Er0 = − 2mc 2
4n
l+1/2 −3

2
h i
0 0 En n(j(j+1)−l(l+1−3/4))
ĤSO Not Diagonal No Diagonal Yes No ESO = mc2 l(l+1)(l+1/2)

2
h i
En
16

Ĥf0 s = Not Diagonal No Diagonal Yes No Ef0 s = − 2mc 2

4n
(j+1/2) −3
Ĥr0 + ĤSO
0
II. Determining a “GOOD” Angular Basis and Corrections to the Energies
for ONLY the Zeeman Perturbation ĤZ0 .

Zeeman Effect

6.8 Finding a “GOOD” Angular Basis for the Zeeman term as a Perturbation for the Hydrogen Atom
Note: Treating the Zeeman term as the only perturbation on the unperturbed Hamiltonian is a hypothetical
case, one should always consider both the Zeeman term and the fine structure term when an external magnetic
field is applied to the hydrogen atom. This hypothetical case is presented here to help when later we consider
both the fine structure term and the Zeeman term as perturbations for the hydrogen atom.
2
e2 1
• A perturbation ĤZ0 acts on a hydrogen atom with the unperturbed Hamiltonian Ĥ 0 = − 2m
h̄
∇2 − 4π0 r .
The Zeeman perturbation term in the Hamiltonian is
e ~ ~ ext = µB Bext (L̂z + 2Ŝz )
ĤZ0 = ~ ·B
(L + 2S) (15)
2m h̄
~ ext = Bext ẑ.
in which B

4. In each degenerate subspace of Ĥ 0 , the off-diagonal matrix elements of ĤZ0 will be zero in a “good”
basis. Is a “good” angular basis for finding the corrections to the energies the coupled representation, the
uncoupled representation, or any arbitrary complete orthonormal basis found with linear combinations of
the coupled or uncoupled states with the same principal quantum number n? Explain.

Consider the following conversation regarding choosing a “good” basis when the perturbation is
ĤZ0 = µB B
h̄
ext
(L̂z + 2Ŝz ).
Student 1: When a perturbation ĤZ0 = µB Bext (L̂z + 2Ŝz ) acts on a hydrogen atom, the uncoupled represen-
tation is a “good” angular basis for finding the first order corrections to the energies.
Student 2: I disagree. We can use either the coupled or the uncoupled representation to find the first order
corrections to the energies. Since JˆZ = L̂z + Ŝz , the perturbation ĤZ0 = µB Bext (L̂z + 2Ŝz ) is not much different
from JˆZ and so the coupled representation is also a “good” angular basis.
Student 3: I only agree with Student 1. JˆZ is diagonal in both the coupled and the uncoupled representation.
However, Ĥ 0 = µB Bext (L̂z +2Ŝz ) = µB Bex (Jˆz +Ŝz ) is not proportional to Jˆz . Therefore, ĤZ0 = µB Bext (L̂z +2Ŝz )
is only diagonal in the uncoupled representation in which the basis states are eigenstates of L̂z and Ŝz .

Explain why you agree or disagree with each student.

(If you need further help with why L̂z + 2Ŝz is diagonal in the uncoupled representation and not the coupled
representation, refer to the Part I of this tutorial.)

17
** Check your answer to question 4. **

4. The uncoupled representation forms a “good” basis for finding the corrections to the energies of the
hydrogen atom due to only the Zeeman term ĤZ0 .

If your answer to question 4 does not match with the checkpoint, go back and reconcile any differences.

6.9 First Order Corrections to the Energy Spectrum of the Hydrogen Atom in Perturbation Theory Due to
the Zeeman Term
Student 1 and Student 3 are correct in the preceding conversation in stating that the uncoupled representation
will form a “good” angular basis for ĤZ0 on Ĥ 0 .

5. What are the first order corrections to the energies due to the Zeeman term ĤZ0 using a “good” basis?

6. How many distinct energies does the n = 2 state split into when we take into account ĤZ0 as a perturbation
on Ĥ 0 ? Explain. [Hint: How many possible values of ml + 2ms are there for n = 2?]

18
** Check your answer to questions 5-6. **

5. The first order corrections to the energies due to only the Zeeman term ĤZ0 using a “good” basis (the
uncoupled representation) is given by

EZ0 = µB Bext (ml + 2ms ) (16)

6. There are 5 distinct energies. For the n = 2 subspace, there are three possible values of ml (−1, 0, 1)
for l = 1 and one possible values of ml (0) for l = 0. For each value of l, there are two possible values of
ms ( 21 , − 12 ).

l ml ms Energy (EZ0 )
1
−1 2 0
−1 − 12 −2µB Bext
0 − 12 −µB Bext
1 1
0 2 µB Bext
1 − 12 0
1
1 2 2µB Bext
0 − 12 −µB Bext
0 1
0 2 µB Bext

If your answers to questions 5 and 6 do not match with the checkpoint, go back and reconcile any differences.

In one to two sentences, summarize what you have learned about the “good” states for finding the first order
corrections to the energy spectrum of the hydrogen atom due to only the Zeeman term ĤZ0 (pertaining to
whether the coupled representation, the uncoupled representation, or any arbitrary complete orthonormal basis
found with linear combinations of states with a fixed principal quantum number n in the coupled or uncoupled
representation form a “good” basis).

19
Summary: Finding a “GOOD” Angular Basis for Various Perturbations on Ĥ 0

• ĤZ0 is diagonal in each degenerate subspace of Ĥ0 in the uncoupled representation.

– The basis states in the uncoupled representation are eigenstates of L̂z and Ŝz

• The uncoupled representation forms a “good” angular basis for finding the corrections to the energies due to the Zeeman pertrubation ĤZ0 .

Hamiltonian Uncoupled Is the Uncoupled Coupled Is the Coupled Is Any Arbitrary Complete Orthonormal Energy
Representation Representation Representation Representation Basis Constructed with Linear Combination
(for a fixed n) a “Good” Basis? (for a fixed n) a “Good” Basis? of a Complete Set of States with the
Same n and l in the Coupled or Uncoupled
Representation a “Good” Basis?

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

2
h i
En
Ĥr0 Diagonal Yes Diagonal Yes Yes Er0 = − 2mc 2
4n
l+1/2 −3
20

2
h i
0 0 En n(j(j+1)−l(l+1−3/4))
ĤSO Not Diagonal No Diagonal Yes No ESO = mc2 l(l+1)(l+1/2)

2
h i
En
Ĥf0 s = Not Diagonal No Diagonal Yes No Ef0 s = − 2mc 2
4n
(j+1/2) −3
Ĥr0 + ĤSO
0

ĤZ0 Diagonal Yes Not Diagonal No No EZ0 = µBext (ml + 2ms )

III. Determining a “GOOD” Angular Basis and Corrections to the Energies
due to BOTH the Fine Structure and the Zeeman Perturbations Ĥ 0 = Ĥf0 s +
ĤZ0 .
As we work through the remainder of the tutorial, we will fill in the following flowchart after each section
regarding the intermediate, strong, and weak field Zeeman effect.

Determining a “GOOD” Angular Basis and Corrections to the Energies due to

BOTH the Fine Structure and Zeeman Terms
Which term in Ĥ 0 = Ĥf0 s + ĤZ0 is stronger?

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

(Zeeman Term is Stronger) (Both Terms are Comparable) (Fine Structure Term is Stronger)

Strong Field Intermediate Field Weak Field

Zeeman Effect Zeeman Effect Zeeman Effect

21
CASE 1: Intermediate Field Zeeman Effect (Ef0 s ≈ EZ0 ), when the fine structure term is compa-
rable to the Zeeman term in Ĥ 0 )

6.10 Finding a “Good” Angular Basis for the Intermediate Field Zeeman Effect
Consider the following conversation regarding whether the coupled or uncoupled representation forms a “good”
angular basis for the intermediate field Zeeman effect (in order to find the first order corrections to the energies).
Student 1: In the intermediate field Zeeman effect, we must treat Ĥf0 s and ĤZ0 on an equal footing. Does the
coupled or uncoupled representation form a “good” angular basis?
Student 2: Since the coupled representation is a “good” angular basis for the fine structure term and the
uncoupled representation is a “good” angular basis for the Zeeman term, both the coupled and uncoupled
representation form “good” angular bases and are equally appropriate to find the first order corrections to the
energies for Ĥ 0 = Ĥf0 s + ĤZ0 .
Student 3: I disagree with Student 2. You cannot consider different bases for different parts of Ĥ 0 . If we choose
the coupled representation, Ĥ 0 = Ĥf0 s + ĤZ0 is not diagonal in each degenerate subspace of Ĥ 0 since ĤZ0 is not
diagonal in the coupled representation. Similarly, if we choose the uncoupled representation, Ĥ 0 = Ĥf0 s + ĤZ0 ,
is not diagonal in each degenerate subspace of Ĥ 0 since Ĥf0 s is not diagonal in the uncoupled representation.
Neither of these representations forms a “good” basis.

Explain why you agree or disagree with Student 2 or Student 3.

Consider the following conversation regarding whether to choose the coupled representation or uncoupled rep-
resentation as the angular basis for finding the corrections to the energies in the intermediate field Zeeman
effect.
Student 1: In the intermediate field Zeeman effect, neither the coupled nor uncoupled representation forms a
“good” angular basis. How do we determine the “good” angular basis?
Student 2: We can express Ĥ 0 = Ĥf0 s + ĤZ0 initially in either the coupled or uncoupled representation, which
will not be a “good” angular basis. Then, a “good” angular basis is found by diagonalizing Ĥ 0 in each degener-
ate subspace of Ĥ 0 . Thus, the “good” angular basis states will be linear combinations of the originally chosen
angular basis states.

Do you agree with Student 2? Explain.

22
The angular basis states for n = 2 are listed below in the coupled representation (left), and each state in the
coupled representation is given in terms of a linear combination of states in the uncoupled representation (right)
using the Clebsch-Gordon table (s = 1/2).

Coupled Representation Uncoupled Representation

|l, j, mj i |l, ml i|s, ms i

1 1 1 1
|ψ1 i 0, , |0, 0i ,
2 2 2 2

1 1 1 1
|ψ2 i 0, , − |0, 0i , −
2 2 2 2

3 3 1 1
|ψ3 i 1, , |1, 1i ,
2 2 2 2

3 3 1 1
|ψ4 i 1, , − |1, −1i , −
2 2 2 2

r r
3 1 2 1 1 1 1 1
|ψ5 i 1, , |1, 0i , + |1, 1i , −
2 2 3 2 2 3 2 2

r r
1 1 1 1 1 2 1 1
|ψ6 i 1, , − |1, 0i , + |1, 1i , −
2 2 3 2 2 3 2 2

r r
3 1 1 1 1 2 1 1
|ψ7 i 1, , − |1, −1i , + |1, 0i , −
2 2 3 2 2 3 2 2

r r
1 1 2 1 1 1 1 1
|ψ8 i 1, , − − |1, −1i , + |1 0i , −
2 2 3 2 2 3 2 2

Using the table above, the perturbing Hamiltonian Ĥ 0 = ĤZ0 + Ĥf0 s in the coupled representation is given on
2 2
the next page, in which γ = α8 13.6 eV, α = 4πe0 h̄c , β = µB Bext and the angular basis states are chosen
in the order |ψ1 i = |0, 12 , 12 i, |ψ2 i = |0, 21 , − 12 i, |ψ3 i = |1, 32 , 32 i, |ψ4 i = |1, 32 , − 23 i, |ψ5 i = |1, 32 , 12 i,
|ψ6 i = |1, 12 , 21 i, |ψ7 i = |1, 23 , − 12 i, and |ψ8 i = |1, 12 , − 12 i:

23
 
5γ − β 0 0 0 0 0 0 0

 0 5γ + β 0 0 0 0 0 0 


 0 0 γ − 2β 0 0 0 0 0 


 0 0 0 γ + 2β 0 √
0 0 0 

0
Ĥ = −  2 2
− 3β

 0 0 0 0 γ√ 3 β 0 0 
 
2 1

 0 0 0 0 3 β 5γ − 3 β 0 √
0 

2 2
0 0 0 0 0 0 γ√
+ 3β 3 β
 
 
2
0 0 0 0 0 0 3 β 5γ + 13 β

Consider the following conversation regarding diagonalizing the Ĥ 0 = Ĥf0 s + ĤZ0 matrix in the n = 2 degenerate
subspace of Ĥ 0 for the intermediate field Zeeman effect.
Student 1: In the case of n = 2, Ĥ 0 possesses an eight-fold degeneracy, which means that in order to find a
“good” angular basis for the correction to the n = 2 energy spectrum, we must diagonalize the entire 8 x 8 Ĥ 0
matrix in the n = 2 degenerate subspace of Ĥ 0 .
Student 2: While it is true that we must diagonalize the Ĥ 0 matrix in the degenerate subspace of Ĥ 0 , we are
fortunate that the symmetry of the hydrogen atom yields many zero off-diagonal matrix elements. Therefore,
Ĥ 0 will be block diagonal in the degenerate subspaces of Ĥ 0 .
Student 3: I agree with Student 2. We must make an effort to diagonalize Ĥ 0 only in those block diagonal
subspaces with smaller dimensions than the original 8×8 Ĥ 0 matrix in order to diagonalize the entire Ĥ 0 matrix
in the degenerate subspace of Ĥ 0 to obtain the “good” angular basis set.
Student 4: I agree with Student 1, Student 2, and Student 3. When I calculate the Ĥ 0 matrix for n = 2 in the
coupled representation and the angular basis states are chosen in the order |ψ1 i = |0, 12 , 12 i, |ψ2 i = |0, 21 , − 12 i,
|ψ3 i = |1, 32 , 23 i, |ψ4 i = |1, 32 , − 23 i, |ψ5 i = |1, 23 , 12 i, |ψ6 i = |1, 12 , 21 i, |ψ7 i = |1, 32 , − 12 i, and |ψ8 i = |1, 12 , − 12 i,
I get the block diagonal matrix Ĥ 0 below
 
5γ − β 0 0 0 0 0 0 0

 0 5γ + β 0 0 0 0 0 0 


 0 0 γ − 2β 0 0 0 0 0 


 0 0 0 γ + 2β 0 √
0 0 0 

Ĥ 0 = −  0 0 0 0 γ√ − 3β2 2 
3 β 0 0

 
 
2 1

 0 0 0 0 3 β 5γ − 3 β 0 √
0 
2 2 
0 0 0 0 0 0 γ√+ 3β 3 β
 
 
2 1
0 0 0 0 0 0 3 β 5γ + 3 β
" √ # " √ #
2 2
γ√− 32 β 3 β γ +
√ 3
2
β 3 β
We will only need to diagonalize the 2 × 2 matrices − 2 1
and − 2
to
3 β 5γ − 3 β 3 β 5γ + 31 β
obtain the “good” angular basis.

Explain why you agree or disagree with each student.

24
6.11 First Order Corrections to the Energy Spectrum of the Hydrogen Atom in Perturbation Theory for the
Intermediate Field Zeeman Effect
Consider the following conversation regarding whether choosing the coupled representation or the uncoupled
representation as the initial angular basis and then carrying out a change of basis by diagonalizing Ĥ 0 in the
degenerate subspace of Ĥ 0 affects the corrections to the energies in the intermediate field Zeeman effect.
Student 1: When calculating the first order corrections to the energies in the intermediate field Zeeman effect,
we can choose either the coupled or the uncoupled representation as the initial angular basis even if we know
it is not a “good” angular basis. Then, a “good” angular basis will be found by diagonalizing Ĥ 0 in each
degenerate subspace of Ĥ 0 . After diagonalizing Ĥ 0 , the new basis is “good” and the first order corrections to
the energies are the diagonal matrix elements.
Student 2: I disagree. Since the diagonal matrix elements of Ĥ 0 will depend on the choice of initial basis, a
different choice of the initial basis in which we diagonalize Ĥ 0 in the degenerate subspace of Ĥ 0 will change the
first order corrections to the energies.
Student 3: I disagree with Student 2. After diagonalizing Ĥ 0 in each degenerate subspace of Hˆ0 , a “good”
basis is obtained and the first order correction to the energy will be the same regardless of which basis, e.g.,
the coupled or uncoupled representation, you had initially chosen. In a “good” basis, you will end up with the
same diagonal matrix elements of Ĥ 0 which are the first order corrections to the energies.

Explain why you agree or disagree with each student.

In one or two sentences, summarize what you have learned about the “good” angular basis states for finding
the first order corrections to the energy spectrum of the hydrogen atom due to the intermediate field Zeeman
effect (pertaining to whether the coupled representation, the uncoupled representation, or any arbitrary com-
plete orthonormal basis constructed with linear combinations of a complete set of states with a fixed principal
quantum number n in the coupled or uncoupled representation form a “good” angular basis).

Shortly, we shall calculate the first order corrections to the energies due to the intermediate field Zeeman ef-
fect. But before we do so, let’s first consider the limiting cases when one perturbation is stronger than the other.

25
Review the following flowchart concerning a “good” angular basis and corrections to the energies for the
intermediate field Zeeman effect. Using the intermediate field Zeeman effect as a guide, attempt to fill in the
steps required to determine a “good” angular basis and corrections to the energies due to both the fine structure
(Ĥf0 s ) and Zeeman (ĤZ0 ) terms for the strong field Zeeman effect (EZ0 Ef0 s ) and the weak field Zeeman effect
(Ef0 s EZ0 ). You can add or remove boxes in the flowchart if necessary.

Determining a “GOOD” Angular Basis and Corrections to the Energies due to

BOTH the Fine Structure and Zeeman Term
Which term in Ĥ 0 = Ĥf0 s + ĤZ0 is stronger?

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

(Zeeman Term is Stronger) (Both Terms are Comparable) (Fine Structure Term is Stronger)

Strong Field Intermediate Field Weak Field

Zeeman Effect Zeeman Effect Zeeman Effect

Neither the coupled nor the

uncoupled representation
form a “good” angular basis.

Choose either the coupled or the

uncoupled representation as the ini-
tial basis to write Ĥ 0 = Ĥf0 s + ĤZ0
(although neither is a “good” basis).

Diagonalize Ĥ 0 = Ĥf0 s + ĤZ0

in each degenerate subspace of
Ĥ 0 to obtain a “good” basis.

In the “good” basis, the diagonal matrix

elements of Ĥ 0 = Ĥf0 s + ĤZ0 are the
first order corrections to the energies.

26
Summary: Finding a “GOOD” Angular Basis for the Intermediate Field Zeeman
Effect Ĥ 0 = ĤZ0 + Ĥf0 s

• Neither the coupled nor the uncoupled representation forms a “good” angular basis when EZ0 ≈ Ef0 s .

• To find a “good” angular basis for the intermediate field Zeeman effect EZ0 ≈ Ef0 s :

– First choose either the coupled or the uncoupled representation as the basis.
– Diagonalize Ĥ 0 = ĤZ0 + Ĥf0 s in each degenerate subspace of Ĥ 0 .
– The “good” basis will be a special linear combinations of the originally chosen basis set.

27
6.12 Limiting Cases
Consider the following conversation regarding finding a “good” basis when treating the perturbation in two
steps.
Student 1: If we have a perturbation that has two terms in which one perturbation is stronger than the other,
we can first take into account the correction due to the stronger perturbation and then take into account the
weaker perturbation as a second perturbation.
Student 2: I agree. In the first step, we must find a “good” basis for Ĥ 0 and Ĥstrong0 0
, so Ĥstrong must be
0 0 0 0
diagonal in each degenerate subspace of Ĥ . Then in the second step, treat Ĥstrong = Ĥ + Ĥstrong as the
unperturbed Hamiltonian and Ĥweak0 0
as perturbation on Ĥstrong 0
= Ĥ 0 + Ĥstrong . A “good” basis for step 2 is
0 0 0 0
one in which Ĥweak is diagonal in each degenerate subspace of Ĥstrong = Ĥ + Ĥstrong .
Student 3: I disagree with Student 2. You cannot find one “good” basis for step 1 and a different “good”
basis for step 2.
Student 4: I agree with Student 1 and Student 2. It is approprate to use a two step perturbation theory when
one part of the perturbation is stronger than another if the error due to this two step process is negligible. If
0
the basis after step 1 is not a “good” basis for step 2, we would need to diagonalize Ĥweak in each degenerate
0 0 0
subspace of Ĥstrong = Ĥ + Ĥstrong to find a “good” basis in step 2.

Explain why you agree or disagree with each student.

• Summary of Two-Step Approximation

0
– STEP 1: First consider only the stronger perturbation Ĥstrong as a perturbation on Ĥ 0 .
0
∗ Choose a basis in which Ĥ 0 is diagonal and Ĥstrong is diagonal in each degenerate subspace of
0
Ĥ .
0
∗ Determine the first order corrections to the energies Estrong due to the stronger perturbation
0
Ĥstrong .
0
– STEP 2: Consider the weaker perturbation Ĥweak as a perturbation on the new unperturbed
0 0 0
Hamiltonian Ĥstrong = Ĥ + Ĥstrong .
0
∗ Treat as the new unperturbed Hamiltonian Ĥstrong 0
= Ĥ 0 + Ĥstrong .
0 0 0
∗ Treat Estrong = E + Estrong as the new unperturbed energies.
0
∗ Determine the degeneracy of Ĥstrong 0
= Ĥ 0 + Ĥstrong (i.e., how many distinct states have the
0
same energy Estrong,i ).
0
∗ Determine if Ĥweak 0
is diagonal in each degenerate subspace of Ĥstrong 0
= Ĥ 0 + Ĥstrong .
0
· If Ĥweak 0
is already diagonal in each degenerate subspace of Ĥstrong 0
= Ĥ 0 + Ĥstrong then the
0 0
basis is “good” and the diagonal elements of Ĥweak will give the corrections Eweak .
0
· If Ĥweak 0
is not diagonal in each degenerate subspace of Ĥstrong 0
= Ĥ 0 + Ĥstrong , diagonalize
0 0
Ĥweak in each degenerate subspace of Ĥstrong to find a “good” basis.

28
Consider the following conversation regarding approximating the corrections to the energy when one perturba-
tion is stronger than the other.
Student 1: When the hydrogen atom is placed in an external magnetic field, we must consider both the
Zeeman term and the fine structure term in the Hamiltonian as perturbations. Therefore, neither the coupled
nor the uncoupled representation form a “good” basis. We must diagonalize the entire Ĥ 0 = ĤZ0 + Ĥf0 s matrix
in the degenerate subspace of Ĥ 0 .
Student 2: That is true. However, if one term is much stronger than the other, we can approximate the
first order corrections to the energy using perturbation theory in two steps. In the first step, consider only the
stronger perturbation. Then, as the second step, consider the weaker perturbation. This two-step approxima-
tion may simplify the process for finding a “good” basis and provide an alternative to diagonalizing the entire
Ĥ 0 = ĤZ0 + Ĥf0 s matrix in each degenerate subspace of Ĥ 0 .
Student 3: I agree with Student 2. We will find that in the limiting case, the first order corrections to the ener-
gies obtained using this two-step approximation match with the first order corrections to the energies obtained
by diagonalizing the entire Ĥ 0 = ĤZ0 + Ĥf0 s matrix in each degenerate subspace of Ĥ 0 as in the intermediate
field Zeeman effect when we take the appropriate limit.

Explain why you agree or disagree with each student.

All the students are correct in the preceding conversation. However, we will focus on the limiting cases and use
the method described by Student 2 and Student 3.

• When EZ0 Ef0 s or Ef0 s EZ0 , we can use a two step approximation to find the first order corrections
to the energies of the hydrogen atom.

• Two-Step Approximation for the Strong and Weak Field Zeeman Effect

– CASE 2: Strong Field Zeeman Effect (EZ0 Ef0 s )

∗ The Zeeman term dominates.
· STEP 1: Treat only ĤZ0 as the perturbation on Ĥ 0 .
· STEP 2: Now, treat Ĥf0 s as the perturbation on the new unperturbed Hamiltonian ĤZ0 =
Ĥ 0 + ĤZ0 after the first step.
– CASE 3: Weak Field Zeeman Effect (Ef0 s EZ0 )
∗ The fine structure term dominates.
· STEP 1: Treat only Ĥf0 s as the perturbation on Ĥ 0 .
· STEP 2: Now, treat ĤZ0 as the perturbation on the new unperturbed Hamiltonian Ĥf0s =
Ĥ 0 + Ĥf0 s after the first step.

29
CASE 2: Strong Field Zeeman Effect: Perturbation Theory in Two Steps to Find the Corrections
to Energy Spectrum

6.12.1 Finding a “GOOD” Basis for the Strong Field Zeeman Effect in the Hydrogen Atom
STEP 1:
For the case EZ0 Ef0 s , in step 1, we treat only ĤZ0 as the perturbation on Ĥ 0 .

7. For the case EZ0 Ef0 s , what is a “good” angular basis for step 1 when we only consider ĤZ0 as pertur-
bation? Explain.

8. Write an expression for the first order corrections to the energies due to only the stronger perturbation
ĤZ0 acting on the unperturbed Hamiltonian Ĥ 0 (once you have found a “good” basis). Here the first
order corrections are the exact results for the energies for the Hamiltonian Ĥ = Ĥ 0 + ĤZ0 after STEP 1
since Ĥ 0 and ĤZ0 commute (so Ĥ 0 and ĤZ0 can be diagonalized simultaneously in a “good” basis).

STEP 2:
In the strong field when EZ0 Ef0 s , in step 2, the unperturbed Hamiltonian includes the Zeeman term and
becomes
h̄2 2 e2 e
ĤZ0 = Ĥ 0 + ĤZ0 = − ∇ − + Bext (L̂z + 2Ŝz ). (17)
2m 4π0 r 2m

9. Is the ĤZ0 matrix a diagonal matrix if the coupled representation or the uncoupled representation is chosen
as the basis? Explain your reasoning. Your answer should be consistent with your response to question
7 above.

Now for the n = 2 subspace, take a look at the ĤZ0 = Ĥ 0 + ĤZ0 and Ĥf0 s matrices given below in which
E2 = − 13.6eV
4 and the basis vectors are chosen in the uncoupled representation (|l, ml , ms i) in the order
|ψ1 i = |0, 0, 2 i, ψ2 i = |1, 0, − 21 i, |ψ3 i = |1, 1, 12 i, |ψ4 i = |1, 1, − 12 i, |ψ5 i = |1, 0, 12 i, |ψ6 i = |1, 0, − 12 i,
1

|ψ7 i = |1, −1, 12 i, and |ψ8 i = |1, −1, − 21 i. Then answer questions 10-13 for the Strong field Zeeman effect.

   
1 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0

 0 1 0 0 0 0 0 0 


 0 −1 0 0 0 0 0 0 


 0 0 1 0 0 0 0 0 


 0 0 2 0 0 0 0 0 

0 0 0 13.6eV  0 0 0 1 0 0 0 0   0 0 0 0 0 0 0 0 
ĤZ = Ĥ + ĤZ = −   + µB Bext  
4 
 0 0 0 0 1 0 0 0 


 0 0 0 0 1 0 0 0 


 0 0 0 0 0 1 0 0 


 0 0 0 0 0 −1 0 0 

 0 0 0 0 0 0 1 0   0 0 0 0 0 0 0 0 
0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 −2

30
 
E2 + µB Bext 0 0 0 0 0 0 0

 0 E2 − µB Bext 0 0 0 0 0 0 


 0 0 E2 + 2µB Bext 0 0 0 0 0 

ˆ0
 0 0 0 E2 0 0 0 0 
HZ =  

 0 0 0 0 E2 + µB Bext 0 0 0 


 0 0 0 0 0 E2 − µB Bext 0 0 

 0 0 0 0 0 0 E2 0 
0 0 0 0 0 0 0 E2 − 2µB Bext
(18)
 
15 0 0 0 0 0 0 0
 0 15 0 0 0 0 0 0 
 
 0 0 3 0 0 0 0 0 
2
 √ 
(−13.6 eV)α  0 0 0 11 4 2 0 0 0 
Ĥf0 s = Ĥr0 + ĤSO
0
= Ĥf0 s = √ (19)
 
192  0 0 0 4 2 7 0 0 0 
 
√
 0 0 0 0 0 7 4 2 0 
 
 √ 
 0 0 0 0 0 4 2 11 0 
0 0 0 0 0 0 0 3

10. Determine the degeneracy in the energy eigenvalues of the “new” unperturbed Hamiltonian ĤZ0 = Ĥ 0 +ĤZ0
after accounting for the stronger perturbation. Then circle the corresponding degenerate subspaces of
ĤZ0 = Ĥ 0 + ĤZ0 (for the n = 2 subspace) in the preceding matrix representation in equation (18).

11. Identify the matrix elements of Ĥf0 s in equation (19) that correspond to each degenerate subspace of
ĤZ0 = Ĥ 0 + ĤZ0 in equation (18) and determine whether Ĥf0 s is diagonal in each of these subspaces of ĤZ0 .

12. Determine whether the uncoupled representation chosen as the basis in question 9 is a “good” basis for
the unperturbed Hamiltonian ĤZ0 = Ĥ 0 + ĤZ0 and the perturbation Ĥf0 s . Explain how you made the
determination.

31
** Check your answers to questions 7-10. **

7. The uncoupled representation forms a “good” basis when only the Zeeman term ĤZ0 is the perturbation
on the unperturbed Hamiltonian Ĥ 0 .
8. As we determined in equation (16), the first order corrections to the energies due to the Zeeman term
ĤZ0 in the uncoupled representation are EZ0 = µB Bext (ml + 2ms ).
9. ĤZ0 = Ĥ 0 + ĤZ0 is diagonal if the uncoupled representation is chosen as the basis.
10. ĤZ0 = Ĥ 0 + ĤZ0 possesses three two-fold degeneracies (see equation 18) in the n = 2 subspace of Ĥ 0 .
There are two distinct states that share the new unperturbed energies E2 + µBext , E2 − µBext , and E2 .
11. The perturbation Ĥf0 s is diagonal in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 treated as the
unperturbed Hamiltonian in step 2 of perturbation theory.
12. Yes. The uncoupled representation is a “good” angular basis in this case since ĤZ0 = Ĥ 0 + ĤZ0 is
diagonal and Ĥf0 s is diagonal in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 .

If your answers to questions 7-12 do not match with the checkpoint answers, go back and reconcile any differ-
ences.

For the following conversation, consider the n = 2 subspace for which the unperturbed Hamiltonian for the
strong field Zeeman effect is ĤZ0 = Ĥ 0 + ĤZ0 after the first step for the strong field Zeeman effect (EZ0 Ef0 s ).
Student 1: In the limit EZ0 Ef0 s , we can only take the Zeeman term ĤZ0 as the perturbation first when
we are using the two-step approximation. Then, after the first step, consider the unperturbed Hamiltonian as
ĤZ0 = Ĥ 0 + ĤZ0 with unperturbed energies En0 = En + µBext (ml + 2ms ), and consider the degeneracy left in
En0 to determine the degenerate subspaces of ĤZ0 . In the second step, treat the fine structure part Ĥf0 s as the
perturbation on ĤZ0 = Ĥ 0 + ĤZ0 .
Student 2: What is the degeneracy left in the hydrogen atom energy spectrum when it is placed in a strong
external magnetic field after accounting for only the Zeeman term ĤZ0 as the perturbation in the first step?
Student 3: In the n = 2 subspace, the ĤZ0 = Ĥ 0 + ĤZ0 matrix is the following if the basis states are chosen in
the uncoupled representation (|l, ml , ms i) in the order |ψ1 i = |0, 0, 12 i, |ψ2 i = |0, 0, − 21 i,|ψ3 i = |1, 1, 21 i,
|ψ4 i = |1, 1, − 12 i, |ψ5 i = |1, 0, 21 i, |ψ6 i = |1, 0, − 12 i, |ψ7 i = |1, −1, 12 i, and |ψ8 i = |1, −1, − 12 i
 
E2 + µB Bext 0 0 0 0 0 0 0
0 E2 − µB Bext 0 0 0 0 0 0
 
 
0 0 E2 + 2µB Bext 0 0 0 0 0
 
 
 
 0 0 0 E2 0 0 0 0 
ˆ 0
HZ = 
 
.

 0 0 0 0 E2 + µB Bext 0 0 0 

0 0 0 0 0 E2 − µB Bext 0 0
 
 
 

 0 0 0 0 0 0 E2 0 

0 0 0 0 0 0 0 E2 − 2µB Bext

ĤZ0 = Ĥ 0 + ĤZ0 has three separate two-fold degeneracies for the energies E2 + µB Bext , E2 − µB Bext , and E2 as
indicated by the boxed, underlined, and circled matrix elements of ĤZ0 above.
Student 4: I agree with both Student 1 and Student 3. By considering the stronger perturbation ĤZ0 first,
some of the degeneracies are broken and the eight-fold degeneracy in the energy spectrum of Ĥ 0 has become
three separate two-fold degeneracies plus two nondegenerate levels in the energy spectrum of ĤZ0 = Ĥ 0 + ĤZ0 .

Explain why you agree or disagree with each student.

32
Consider the following conversation regarding the case EZ0 Ef0 s and treating the perturbation in two steps
with the stronger Zeeman term considered as part of the unperturbed Hamiltonian ĤZ0 = Ĥ 0 + ĤZ0 to find the
corrections due to the weaker perturbation Ĥf0 s .
Student 1: Even in a two step process, how can we find a “good” basis easily when both the fine structure
term Ĥf0 s and the Zeeman term ĤZ0 are present? The “good” basis is one in which there are no off-diagonal
matrix elements of Ĥ 0 = ĤZ0 + Ĥf0 s in the degenerate subspace of Ĥ 0 . Since Ĥf0 s is diagonal in the coupled
representation and ĤZ0 is diagonal in the uncoupled representation, neither the coupled nor the uncoupled
representation could possibly form a “good” basis when we have Ĥ 0 = ĤZ0 + Ĥf0 s .
Student 2: I agree. In step 1, when we only consider ĤZ0 as the perturbation on Ĥ 0 , we choose the uncoupled
representation as the “good” basis. Once the uncoupled representation is chosen as the “good” basis, we are
guaranteed to have off-diagonal matrix elements in the weaker fine structure perturbation matrix Ĥf0 s . Thus,
the “good” basis for step 1 cannot be a “good” basis for step 2.
Student 3: Actually, once we treat the stronger Zeeman perturbation ĤZ0 in the first step, we lift some
of the degeneracy in the energy spectrum of Ĥ 0 . There is still degeneracy in the energy spectrum En0 =
En + µB Bext (ml + 2ms ) after the first step, but now the degeneracy is present in smaller subspaces of Ĥ 0 . For
example, for the n = 2 subspace in step 2, ĤZ0 = Ĥ 0 + ĤZ0 in the uncoupled representation is
 
E2 + µB Bext 0 0 0 0 0 0 0
0 E2 − µB Bext 0 0 0 0 0 0
 
 
0 0 E2 + 2µB Bext 0 0 0 0 0
 
 
 
 0 0 0 E2 0 0 0 0 
ˆ0
HZ = 
 
.

 0 0 0 0 E2 + µB Bext 0 0 0 

0 0 0 0 0 E2 − µB Bext 0 0
 
 
 

 0 0 0 0 0 0 E2 0 

0 0 0 0 0 0 0 E2 − 2µB Bext

In the uncoupled representation, Ĥf0 s is not diagonal in the entire n = 2 subspace, but it is diagonal in each
degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 . In the Ĥf0 s matrix below, the elements of the degenerate subspace of
ĤZ0 corresponding to the degenerate energy E2 + µB Bext are boxed. We see that Ĥf0 s is diagonal in the 2 × 2
subspace corresponding to the degenerate energy E2 + µB Bext .
 
15 0 0 0 0 0 0 0
 0 15 0 0 0 0 0 0 
 
 0 0 3 0 0 0 0 0 
2
 √ 
(−13.6 eV)α 
0 0 0 11 4 2 0 0 0

Ĥf0 s = √ .
 
192  0 0 0 4 2 7 0 0 0 

 √ 
 0 0 0 0 0 7 4 2 0
√

 
 0 0 0 0 0 4 2 11 0 
0 0 0 0 0 0 0 3

Similarly, Ĥf0 s is diagonal in the degenerate subspace of ĤZ0 for the degenerate energies E2 and E2 − µB Bext .
Therefore, the uncoupled representation does form a “good” basis in this two step process.

Explain why you agree or disagree with each student.

33
Consider the following conversation regarding choosing the basis states in a different order to easily determine
a “good” basis for the strong field Zeeman effect (EZ0 Ef0 s ).
Student 1: In the strong field Zeeman effect, for the n = 2 subspace, we chose basis states in the uncoupled
representation (|l, ml , ms i) in the order |ψ1 i = |0, 0, 12 i, |ψ2 i = |0, 0, − 12 i,|ψ3 i = |1, 1, 12 i, |ψ4 i = |1, 1, − 12 i,
|ψ5 i = |1, 0, 12 i, |ψ6 i = |1, 0, − 21 i, |ψ7 i = |1, −1, 12 i, and |ψ8 i = |1, −1, − 12 i to write the ĤZ0 = Ĥ 0 + ĤZ0
matrix in equation (18) and the Ĥf0 s matrix in equation (19). Can we choose to write the basis states in a
different order to make the ĤZ0 = Ĥ 0 + ĤZ0 matrix such that the degenerate eigenvalues along the diagonal are
adjacent? Doing so may make it easier to determine if we have a “good” basis.
Student 2: Yes. Suppose we choose the basis states in the order |ψ1 i = |0, 0, 12 i, |ψ2 i = |1, 0, 21 i, |ψ3 i =
|0, 0, − 12 i, |ψ4 i = |1, 0, − 12 i, |ψ5 i = |1, 1, − 12 i, |ψ6 i = |1, −1, 21 i, |ψ7 i = |1, 1, 12 i, and |ψ8 i = |1, −1, − 12 i,
then in the n = 2 subspace, the ĤZ0 = Ĥ 0 + ĤZ0 matrix is
 
 E2 + µB Bext 0 0 0 0 0 0 0 
 

 0 E2 + µB Bext 0 0 0 0 0 0 

0 0 E2 − µB Bext 0 0 0 0 0
 
 
 
HˆZ0 = 
 0 0 0 E2 − µB Bext 0 0 0 0 
.
 

 0 0 0 0 E2 0 0 0 


 0 0 0 0 0 E2 0 0 

 
 0 0 0 0 0 0 E2 + 2µB Bext 0 
 
0 0 0 0 0 0 0 E2 − 2µB Bext
(20)
The degenerate subspaces of ĤZ0= Ĥ 0 + ĤZ0 are boxed. Each degenerate subspace of ĤZ0
is diagonal. Student
3: I agree with Student 2. In order to determine if the “good” basis for step 1 is also a “good” basis for step
2, we must check that Ĥf0 s is diagonal in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 . When basis states are
chosen in the order |φ1 i = |0, 0, 21 i, |φ2 i = |1, 0, 12 i, |φ3 i = |0, 0, − 12 i, |φ4 i = |1, 0, − 12 i, |φ5 i = |1, 1, − 12 i,
|φ6 i = |1, −1, 12 i, |φ7 i = |1, 1, 21 i, and |φ8 i = |1, −1, − 21 i, the Ĥf0 s matrix is
 
 15 0 0 0 0 0 0 0 
 √ 

 0 7 0 0 4 2 0 0 0 

0 0 15 0 0 0 0 0 
 

2 
 √ 
ˆ0 (−13.6eV)α 0 0 0 7 0 4 2 0 0 
Hf s = 
√
 (21)
192  
 0 4 2 0 0 11 0 0 0 
√
 
 

 0 0 0 4 2 0 11 0 0 


 0 0 0 0 0 0 3 0 

0 0 0 0 0 0 0 3

Now we can more easily see that Ĥf0 s is diagonal in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 .
Student 4: I disagree with Student 2 and Student 3. We are not permitted to write the basis states in any
order we choose. If we change the order of the basis states, we change the first order corrections to the energies.
Since the first order corrections to the energies are the diagonal matrix elements of the perturbation in a “good”
basis, writing the basis states in a different order will produce incorrect first order corrections to the energies.
Student 3: No! Reordering the basis states just changes the order in which the unperturbed energies and their
corrections appear, but corrections to each unperturbed energy will be the same. Remember that we need to
reorder both ĤZ0 and Ĥf0 s matrices since the basis vectors must be chosen in the same order for all matrices.

Explain why you agree or disagree with each student.

34
Consider the following conversation regarding the off-diagonal matrix elements of Ĥ 0 f s in each degenerate
subspace of ĤZ0 in the strong field Zeeman effect (EZ0 Ef0 s ).
Student 1: Since ĤZ0 is diagonal in the uncoupled representation and Ĥf0 s is diagonal in the coupled repre-
sentation, we were fortunate that after the first step in our two-step approximation, the off-diagonal matrix
elements of Ĥf0 s were zero in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 in the uncoupled representation after
step 1.
Student 2: I agree with Student 1. Considering ĤZ0 = Ĥ 0 + ĤZ0 as the new unperturbed Hamiltonian after
the first step, the stronger perturbation ĤZ0 breaks some of the degeneracy in the energy spectrum of Ĥ 0 . In
the second step in perturbation theory, the non-zero off-diagonal matrix elements of the weaker perturbation
Ĥf0 s are NOT in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 when we consider the unperturbed Hamiltonian
ĤZ0 = Ĥ 0 + ĤZ0 and the uncoupled representation as the basis.
Student 3: You are correct. We got lucky! After the first step, if the off-diagonal matrix elements of the
weaker perturbation Ĥf0 s were not zero in one or more of the degenerate subspaces of ĤZ0 = Ĥ 0 + ĤZ0 , we would
need to determine the “good” basis by diagonalizing Ĥf0 s in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 in the
second step. The uncoupled representation would not have been a “good” basis.

Explain why you agree or disagree with each student.

6.12.2 Finding Corrections to the Energies for the Strong Field Zeeman Effect
After the first step, the unperturbed Hamiltonian including the Zeeman term is

h̄2 2 e2 e
ĤZ0 = Ĥ 0 + ĤZ0 = − ∇ − + Bext (Lz + 2Sz ) (22)
2m 4π0 r 2m
and the corresponding unperturbed energies are
13.6eV
EZ0 = − + µB Bext (ml + 2ms ) (23)
n2

13. After step 2, find one of the first order corrections to the energies due to the weaker perturbation Ĥf0 s for
the hydrogen atom placed in a strong external magnetic field for the n = 2 subspace.

35
** Check your answers to question 13. **

13. The first order corrections to the energies due to the fine structure term for the hydrogen atom placed
in a strong external magnetic field for the n = 2 subspace are the diagonal elements of Ĥf0 s in equation
(21).

(−13.6 eV)α2 (−13.6 eV)α2

E10 = (15) E20 = (7)
192 192

(−13.6 eV)α2 (−13.6 eV)α2

E30 = (15) E40 = (7)
192 192

(−13.6 eV)α2 (−13.6 eV)α2

E50 = (11) E60 = (11)
192 192

(−13.6 eV)α2 (−13.6 eV)α2

E70 = (3) E80 = (3)
192 192

If your answers to question 13 do not match with the checkpoint answers, go back and reconcile any differences.

In one to two sentences, summarize what you have learned about the “good” angular basis states for finding
the first order corrections to the energy spectrum of the hydrogen atom due to the strong field Zeeman effect
(pertaining to whether the coupled representation, the uncoupled representation, or any arbitrary complete
orthonormal basis constructed with linear combinations of states with a fixed principal quantum number n in
the coupled or uncoupled representation form a “good” angular basis).

36
Summary: Finding a “GOOD” Angular Basis for the Strong Field Zeeman Effect (EZ0 Ef0 s )

• We can use a two step process in perturbation theory to find corrections to the hydrogen atom energy
spectrum when EZ0 Ef0 s .

Step 1: Treat the stronger perturbation ĤZ0 as a perturbation on the unperturbed Hamiltonian Ĥ 0 .
– ĤZ0 is diagonal in the uncoupled representation.
Step 2: Treat the fine structure part of the Hamiltonian, Ĥf0 s , as a perturbation on the new unperturbed
Hamiltonian ĤZ0 = Ĥ 0 + ĤZ0 .
– In the uncoupled representation, Ĥf0 s is diagonal in each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0
(even though Ĥf0 s has off-diagonal matrix elements in the uncoupled representation, they are not in
each degenerate subspace of ĤZ0 = Ĥ 0 + ĤZ0 ).

• The uncoupled representation forms a “good” angular basis for finding the corrections to the energies.

Review the following flowchart concerning the “good” basis and how to find the corrections to the energies for
the intermediate and strong field Zeeman effect. Using the intermediate and strong field Zeeman effect as a
guide, attempt to fill in the steps required to determine a “good” basis and corrections to the energies due to
both the fine structure (Ĥf0 s ) and Zeeman (ĤZ0 ) terms for the the weak field Zeeman effect (Ef0 s EZ0 ). You
may add or remove boxes in the flowchart if necessary.

37
Determining a “GOOD” Angular Basis and Corrections to the Energies due to
BOTH the Fine Structure and Zeeman Effect
Which term in Ĥ 0 = Ĥf0 s + ĤZ0 is stronger?

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

(Zeeman Term is Stronger) (Both Terms are Comparable) (Fine Structure Term is Stronger)

Strong Field Intermediate Field Weak Field

Zeeman Effect Zeeman Effect Zeeman Effect

Neither the coupled nor the

STEP 1: Treat ĤZ0 as
uncoupled representation
a perturbation on Ĥ 0 . forms a “good” angular basis.

Choose either the coupled or the

ĤZ0is diagonal in the un- uncoupled representation as the initial
coupled representation. basis to write Ĥ 0 = Ĥf0 s + ĤZ0 (although
neither is a “good” angular basis).

STEP 2: Consider Ĥ 0 = Ĥf0 s as Diagonalize Ĥ 0 = Ĥf0 s + ĤZ0 in

a perturbation on the unperturbed each degenerate subspace of Ĥ 0
Hamiltonian ĤZ0 = Ĥ 0 + ĤZ0 . to obtain a “good” angular basis.

Ĥf0 s is diagonal in each degener- In the “good” basis, the diagonal matrix
ate subspace of ĤZ0 = Ĥ 0 + ĤZ0 elements of Ĥ 0 = Ĥf0 s + ĤZ0 are the
in the uncoupled representation. first order corrections to the energies.

The uncoupled representation

forms a “good” angular basis.

In the uncoupled representation, the

diagonal matrix elements of Ĥf0 s are the
first order corrections to the energies
CASE 3: Weak Field Zeeman Effect: Perturbation Theory in Two Steps to Find the Corrections
to the Energy Spectrum

6.12.3 Finding a “GOOD” Basis for the Weak Field Zeeman Effect (Ef0 s EZ0 )
STEP 1:
In step 1, for the case Ef0 s EZ0 , we treat only Ĥf0 s as the perturbation on Ĥ 0 .

14. For the case Ef0 s EZ0 , what is the “good” angular basis for step 1 when we ignore ĤZ0 ? Explain.

15. Write an expression for the first order corrections to the energies due to the stronger perturbation Ĥf0 s .

STEP 2:
In the weak field when Ef0 s EZ0 , in step two, the unperturbed Hamiltonian including the fine structure term
becomes
h̄2 2 e2 p̂4
2
0 e 1 ~ ~
Ĥf s = − ∇ − − 3 2
+ S · L. (24)
2m 4π0 r 8m c 8π0 m c2 r3
2

16. For Ĥf0s = Ĥ 0 + Ĥf0 s , is Ĥf0s diagonal if the angular basis is chosen to be the coupled representation,
uncoupled representation, or neither? Explain your reasoning.

Now for the n = 2 subspace, take a look at the Ĥf0s = Ĥ 0 + Ĥf0 s and ĤZ0 matrices given below in the coupled
representation (|l, j, mj i) in which E2 = − 13.6eV 4 and the basis states are chosen in the order |Φ1 i = |1, 32 , 32 i,
|Φ2 i = |1, 32 , 12 i, |Φ3 i = |1, 32 , − 12 i, |Φ4 i = |1, 32 , − 32 i, |Φ5 i = |1, 21 , 12 i, |Φ6 i = |1, 21 , − 12 i, |Φ7 i = |0, 21 , 12 i
and |Φ8 i = |0, 21 , − 21 i. Then, answer questions 16-20 for the weak field Zeeman effect.

Ĥf0s = Ĥ 0 + Ĥf0 s

−1 0
   
1 0 0 0 0 0 0 0 0 0 0 0 0 0

 0 1 0 0 0 0 0 0 


 0 −1 0 0 0 0 0 0 

 0 0 1 0 0 0 0 0   0 0 −1 0 0 0 0 0 
2
   
0 0 0 1 0 0 0 0  + E2 0 0 0 −1 0 0 0 0
Ĥf0s
   
= E2   

 0 0 0 0 1 0 0 0  mc2


 0 0 0 0 −5 0 0 0 


 0 0 0 0 0 1 0 0 


 0 0 0 0 0 −5 0 0 

 0 0 0 0 0 0 1 0   0 0 0 0 0 0 −5 0 
0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 −5

39
E22
 
E2 − mc2
0 0 0 0 0 0 0
 E22 
 0 E2 − mc2
0 0 0 0 0 0 
E22
 
0 0 E2 − 0 0 0 0 0
 
 mc2 
 E22 
0 0 0 E2 − 0 0 0 0
Ĥf0s
 
= mc2  (25)
5E22
0 0 0 0 E2 − 0 0 0
 
 mc2 
 5E22 

 0 0 0 0 0 E2 − mc2
0 0 

5E22
0 0 0 0 0 0 E2 − 0
 
 mc2 
5E22
0 0 0 0 0 0 0 E2 − mc2
 
2 0 0 0 0√ 0 0 0
0 2
0 0 − 32 0√ 0 0
 
 3 
− 23 − 32
 

 0 0 0 0 0 0 

0
 0 0√ 0 −2 0 0 0 0 
ĤZ = µB Bext   (26)

 0 − 32 0√ 0 1
3 0 0 0 

− 32 − 13
 

 0 0 0 0 0 0 

 0 0 0 0 0 0 1 0 
0 0 0 0 0 0 0 −1

17. In step 2, determine the degeneracy of the “new” unperturbed Hamiltonian Ĥf0s = Ĥ 0 + Ĥf0 s after account-
ing for the stronger perturbation and circle the corresponding degenerate subspaces in Ĥf0s = Ĥ 0 + Ĥf0 s
for the n = 2 subspace in the preceding matrix representation in equation (25).

18. Identify the matrix elements of ĤZ0 in equation (26) that correspond to each degenerate subspace of
Ĥf0s = Ĥ 0 + Ĥf0 s in equation (25) and determine whether ĤZ0 is diagonal in each of these subspaces of
Ĥf0s

19. Determine whether the basis chosen in question 16 is a “good” angular basis for the unperturbed Hamil-
tonian Ĥf0s = Ĥ 0 + Ĥf0 s and the perturbation ĤZ0 . Explain how you made the determination.

40
** Check your answers to questions 14-19. **

14. The coupled representation forms a “good” basis when only the fine structure term Ĥf0 s is the
perturbation on the unperturbed Hamiltonian Ĥ 0
15. As we determined in equation (14), the first order corrections tothe energies due to the fine structure
2

E n 4n
term Ĥf0 s in the coupled representation are Ef0 s = 3− .
mc2 j + 1/2
16. For a fixed n, Ĥf0s = Ĥ 0 + Ĥf0 s is diagonal in each degenerate subspace of Ĥ 0 if the coupled
representation is chosen as the angular basis.
17. Ĥf0s = Ĥ 0 + Ĥf0 s possesses two four-fold degeneracies in the n = 2 subspace. There are four distinct
5E 2 E2
states that share the new unperturbed energies E2 − mc22 and E2 − mc22 .
18. The perturbation ĤZ0 is diagonal in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s treated as the
unperturbed Hamiltonian in step 2 of perturbation theory.
19. Yes. The coupled representation is a “good” angular basis. In the second step, the new perturbation
term Ĥf0s = Ĥ 0 + Ĥf0 s is diagonal in the coupled representation for a fixed n and the perturbation ĤZ0 is
diagonal in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s .

If your answers to questions 14-19 do not match with the checkpoint, go back and reconcile any differences.

41
Consider the following conversation regarding the weak field Zeeman effect (Ef0 s EZ0 ) and finding a “good”
basis for the two-step process in the weak field Zeeman effect (Ef0 s EZ0 ).
Student 1: Since ĤZ0 = µB Bext (L̂z + 2Ŝz ), we cannot use the coupled representation as the angular basis. ĤZ0
is not diagonal in the coupled representation. To find the first order corrections to the energies, we must use
the uncoupled representation since ĤZ0 is diagonal in the uncoupled representation.
Student 2: I don’t see how either the coupled or uncoupled representation form a “good” angular basis when
we have both Ĥf0 s and ĤZ0 . They simply cannot be diagonalized simultaneously in either basis. We must choose
linear combinations of the states in the coupled or uncoupled representation so that the basis diagonalizes the
sum of Ĥf0 s and ĤZ0 in each degenerate subspace of Ĥ 0 .
Student 3: I agree with Student 2 only for the intermediate field Zeeman effect with Ef0 s ≈ EZ0 . In the
weak field Zeeman effect in which Ef0 s EZ0 , we can use the two step approximation by considering only the
stronger perturbation Ĥf0 s in the first step. In the second step, we consider the “new” unperturbed Hamiltonian
Ĥf0s = Ĥ 0 + Ĥf0 s and the perturbation ĤZ0 . If the coupled representation is chosen as the angular basis, then in
the n = 2 subspace, the Ĥf0s = Ĥ 0 + Ĥf0 s matrix is (the basis vectors are chosen the same order as in questions
17-19):

 
 E − E22 0 0 0 0 0 0 0 
 2 mc2 
 
 E2 

 0 E2 − mc22 0 0 0 0 0 0 

 2

E
E2 − mc22
 
 0 0 0 0 0 0 0 
 

E 2 
 0 0 0 E2 − mc22 0 0 0 0 
Ĥf0s =
 

 5E 2 

 0 0 0 0 E2 − mc22 0 0 0 

 2

5E
0 0 0 0 0 E2 − mc22 0 0
 
 
 
 5E 2 

 0 0 0 0 0 0 E2 − mc22 0 

 
 5E 2 
0 0 0 0 0 0 0 E2 − mc22

Student 4: I agree with Student 3. ĤZ0 is diagonal in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s shown
for the n = 2 subspace in the following matrix. Therefore, the coupled representation is a “good” basis in the
limit Ef0 s EZ0 . When we use a two step process in the limit Ef0 s EZ0 , some degeneracy is lifted in the first
step.  
 2 0 0 0 0 0 0 0 
 √ 
2 2
0 0 0 − 0 0 0
 
 3 3 
√
 
 2


 0 0 − 23 0 0 − 3 0 0 

 
ĤZ0 = µB Bext 
 0 0 0 −2 0 0 0 0 .

(27)
√
 2 1 

 0 − 3 0 0 3 0 0 0 

 √ 
2

 0 0 − 3 0 0 − 13 0 0 

 

 0 0 0 0 0 0 1 0 

0 0 0 0 0 0 0 −1

Explain why you agree or disagree with each student.

42
Consider the following conversation regarding the off-diagonal matrix elements of ĤZ0 in the degenerate sub-
space of Ĥf0s in the weak field Zeeman effect (Ef0 s EZ0 ).
Student 1: Since ĤZ0 is diagonal in the uncoupled representation and Ĥf0 s is diagonal in the coupled represen-
tation for a fixed n, we were fortunate that, after the first step in our approximation, the off-diagonal matrix
elements of ĤZ0 are zero in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s .
Student 2: I agree with Student 1. The stronger perturbation Ĥf0 s breaks some of the degeneracy in the
energy spectrum of Ĥ 0 . When we consider Ĥf0s = Ĥ 0 + Ĥf0 s as the new unperturbed Hamiltonian in step 2,
the non-zero off-diagonal matrix elements of ĤZ0 are not in the degenerate subspaces of Ĥf0s = Ĥ 0 + Ĥf0 s .
Student 3: You are correct. We got lucky! In step 2, if the off-diagonal matrix elements of the weaker
perturbation ĤZ0 were non-zero in any of the degenerate subspaces of Ĥf0s = Ĥ 0 + Ĥf0 s , we would have needed
to determine the “good” basis by diagonalizing ĤZ0 in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s that is not
diagonal already after the first step.

Explain why you agree or disagree with each student.

6.12.4 Finding Corrections to the Energies for the Weak Field Zeeman Effect (Ef0 s EZ0 )
After the first step, the unperturbed Hamiltonian including the fine structure term is

h̄2 2 e2 p̂4
2
0 e 1 ~ ~
Ĥf s = − ∇ − − 3 2
+ S·L (28)
2m 4π0 r 8m c 8π0 m c2 r3
2

and the corresponding unperturbed energies are

En2

13.6eV 4n
Enjmj =− + 3− (29)
n2 mc2 j + 1/2

20. After step 2, find one of the first order corrections to the energies due to the weaker perturbation ĤZ0 for
the hydrogen atom placed in a weak external magnetic field for the n = 2 subspace.

43
** Check your answers to question 20. **

20. The first order corrections to the energies due to the Zeeman term only for the hydrogen atom placed
in a weak external magnetic field for the n = 2 subspace are the diagonal elements of ĤZ0 in equation (27)

E10 = 2µB Bext

E20 = 2
3 µB Bext
E30 = − 23 µB Bext
E40 = −2µB Bext
E50 = 1
3 µB Bext
E60 = − 13 µB Bext
E70 = µB Bext
E80 = −µB Bext

If your answer to question 20 does not match with the checkpoint, go back and reconcile any differences.

In one to two sentences, summarize what you have learned about the “good” angular basis for finding the first
order corrections to the energy spectrum of the hydrogen atom due to the weak field Zeeman effect (pertaining
to whether the coupled representation, the uncoupled representation, or any arbitrary complete orthonormal
basis constructed with linear combinations of states with a fixed principal quantum number n in the coupled
or uncoupled representation form a “good” angular basis).

44
Summary: Finding a “GOOD” Angular Basis for the Weak Field Zeeman Effect (Ef0 s EZ0 )

• We can use a two step process for perturbation theory to find the corrections to the hydrogen atom energy
spectrum for Ef0 s EZ0 .

Step 1: Treat the stronger perturbation Ĥf0 s as the entire perturbation on the unperturbed Hamiltonian Ĥ 0 .
– Ĥf0 s is diagonal in the coupled representation for a fixed n (in each degenerate subspace of Ĥ 0 ).
Step 2: Treat the Zeeman part of the Hamiltonian, ĤZ0 , as the perturbation on the new unperturbed Hamil-
tonian Ĥf0s = Ĥ 0 + Ĥf0 s .
– In the coupled representation, ĤZ0 is diagonal in each degenerate subspace of Ĥf0s = Ĥ 0 + Ĥf0 s
(even though ĤZ0 has off-diagonal matrix elements in the coupled representation, they are not in the
degenerate subspaces of Ĥf0s = Ĥ 0 + Ĥf0 s ).
– See equation (26) as an example for the n = 2 subspace.

• The coupled representation forms a “good” angular basis for finding the corrections to the energies.

Fill in the following flowchart concerning a “good” angular basis and how to find the corrections to the energies
for the intermediate (Ef0 s ≈ EZ0 ), strong (EZ0 Ef0 s ), and weak field Zeeman effect (Ef0 s EZ0 ).

45
Determining a “GOOD” Angular Basis and Corrections to the Energies Due to
BOTH the Fine Structure and Zeeman Effect
Which term in Ĥ 0 = Ĥf0 s + ĤZ0 is stronger?

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

(Zeeman Term is Stronger) (Both Terms are Comparable) (Fine Structure Term is Stronger)

Strong Field Intermediate Field Weak Field

Zeeman Effect Zeeman Effect Zeeman Effect
Determining a “GOOD” Angular Basis and Corrections to the Energies Due to
BOTH the Fine Structure and Zeeman Effect
Which term in Ĥ 0 = Ĥf0 s + ĤZ0 is stronger?

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

(Zeeman Term is Stronger) (Both Terms are Comparable) (Fine Structure Term is Stronger)

Strong Field Intermediate Field Weak Field

Zeeman Effect Zeeman Effect Zeeman Effect

Neither the coupled nor the

STEP 1: Treat ĤZ0 as STEP 1: Treat Ĥf0 s as
uncoupled representations
a perturbation on Ĥ 0 . form a “good” angular basis. a perturbation on Ĥ 0 .

Choose either the coupled or the

ĤZ0is diagonal in the un- uncoupled representation as the ini- Ĥf0 s is diagonal in the coupled
coupled representation. tial basis to write Ĥ 0 = Ĥf0 s + ĤZ0 representation for a fixed n.
(although neither is a “good” basis).

STEP 2: Consider Ĥ 0 = Ĥf0 s as Diagonalize Ĥ 0 = Ĥf0 s + ĤZ0 STEP 2: Consider Ĥ 0 = ĤZ0 as a

a perturbation on the unperturbed in each degenerate subspace of perturbation on the unperturbed
Hamiltonian ĤZ0 = Ĥ 0 + ĤZ0 . Ĥ 0 to obtain a “good” basis. Hamiltonian Ĥf0s = Ĥ 0 + Ĥf0 s .

Ĥf0 s is diagonal in each degener- In the “good” basis, the diagonal matrix ĤZ0 is diagonal in each degenerate
ate subspace of ĤZ0 = Ĥ 0 + ĤZ0 elements of Ĥ 0 = Ĥf0 s + ĤZ0 are the subspace of Ĥf0s = Ĥ 0 + Ĥf0 s
in the uncoupled representation. first order corrections to the energies. in the coupled representation.

The uncoupled representation The coupled representation

forms a “good” angular basis. forms a “good” angular basis.

In the uncoupled representation, the In the coupled representation, the

diagonal matrix elements of Ĥf0 s are the diagonal matrix elements of ĤZ0 are the
first order corrections to the energies first order corrections to the energies
Fill in the following table for the Strong Field Zeeman Effect.

Strong Field Zeeman Effect

Hamiltonian Is the Matrix Diagonal Is the Uncoupled Is the Matrix Diagonal Is the Coupled Energy/
or Non-Diagonal Representation or Non-Diagonal Representation Energy Correction
in the Uncoupled a “Good” in the Coupled a “Good” (Using the “Good” Basis)
Representation? Basis? Representation? Basis?
(for a fixed n) (for a fixed n)

Unperturbed
Ĥ 0
Step 1
Perturbation
ĤZ0

Unperturbed
ĤZ0 = Ĥ 0 + ĤZ0
48

Step 2
Perturbation
Ĥf0 s
Fill in the following table for the Weak Field Zeeman Effect.

Weak Field Zeeman Effect

Unperturbed
Ĥ 0
Step 1
Perturbation
Ĥf0 s

Unperturbed
49

Ĥf0s = Ĥ 0 + Ĥf0 s
Step 2
Perturbation
ĤZ0
** Check your answers to questions in the preceding tables.**

Strong Field Zeeman Effect

Unperturbed Diagonal Yes, because Diagonal E 0 = − 13.6eV

n2
Step 1 Ĥ 0 ĤZ0 is diagonal No, because
in each degenerate ĤZ0is not diagonal
subspace of Ĥ 0 . in each degenerate
Perturbation Diagonal (actually both Ĥ 0 Non-Diagonal subspace of Ĥ 0 . EZ0 = µB Bext (ml + 2ms )
50

ĤZ0 and ĤZ0 can be

diagonalized
simultaneously
since [Ĥ 0 , ĤZ0 ] = 0).

Unperturbed Diagonal Non-Diagonal EZ0 = E 0 + EZ0

ĤZ0 = Ĥ 0 + ĤZ0 Yes, because No, because = E 0 + µB Bext (ml + 2ms )
Ĥf0 s is diagonal ĤZ0 is not diagonal
Step 2 in each degenerate in each degenerate
Perturbation Non-diagonal subspace of Diagonal subspace of Ĥ 0 . Use Clebsch-Gordon table
Ĥf0 s ĤZ = Ĥ 0 + ĤZ0 .
0 table to express uncoupled states
in the coupled basis
to determine Ef0 s .
Weak Field Zeeman Effect
Hamiltonian Is the Matrix Diagonal Is the Uncoupled Is the Matrix Diagonal Is the Coupled Energy/
or Non-Diagonal Representation or Non-Diagonal Representation Energy Correction
in the Uncoupled a “Good” in the Coupled a “Good” (Using the “Good” Basis)
Representation? Basis? Representation? Basis?
(for a fixed n) (for a fixed n)

Unperturbed Diagonal Diagonal E 0 = − 13.6eV

n2
Step 1 Ĥ 0 No, because Yes, because
Ĥf0 sis not diagonal Ĥf0 s is diagonal
in each degenerate in each degenerate
Perturbation Non-Diagonal subspace of Ĥ 0 . Diagonal subspace of Ĥ 0 . h i
2
En
Ĥf0 s Ef0 s = 2mc2
3− 4n
(j+1/2)

Unperturbed Non-Diagonal Diagonal Ef0s = Eh0 + Ef0 s

2
i
En
Ĥf0s = Ĥ 0 + Ĥf0 s No, because Yes, because = E 0 − 2mc 2
4n
(j+1/2) − 3
Ĥf0 sis not diagonal ĤZ0 is diagonal
Step 2
in each degenerate in each degenerate
Perturbation Diagonal subspace of Ĥ 0 . Non-Diagonal subspace of Use Clebsch-Gordon
ĤZ0 Ĥf s = Ĥ 0 + Ĥf0 s .
0 table to express coupled states
in the uncoupled basis
to determine EZ0
Summary: Finding a “GOOD” Basis for the Zeeman Effect in the Hydrogen Atom

• Intermediate Field Zeeman Effect (EZ0 ≈ Ef0 s )

– Neither the coupled nor the uncoupled representation forms a “good” basis for finding corrections
to the energies.
– One needs to diagonalize Ĥ 0 = ĤZ0 + Ĥf0 s in each degenerate subspace of Ĥ 0 explicitly to find the
“good” basis.

• Strong Field Zeeman Effect (EZ0 Ef0 s )

– We can carry out perturbation theory in two steps.

– The uncoupled representation forms a “good” basis for finding corrections to the energies.

• Weak Field Zeeman Effect (Ef0 s EZ0 )

– We can carry out perturbation theory in two steps.

– The coupled representation forms a “good” basis for finding corrections to the energies.

52
Hamiltonian Uncoupled Is Uncoupled Coupled Is Coupled Is Any ArbitraryComplete Orthonormal Unperturbed First Order
Representation Representation Representation Representation Basis Found with Linear Combinations Energy Correction to
(for a fixed n) a “Good” Basis? (for a fixed n) a “Good” Basis? of a Complete Set of the Coupled the Energy
or Uncoupled States a “Good” Basis?
(with the same n and l)

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

n2
-

2
h i
En
Ĥr0 Diagonal Yes Diagonal Yes Yes En Er0 = − 2mc 2
4n
l+1/2 −3

2
h i
0 0 En n(j(j+1)−l(l+1−3/4))
ĤSO Not Diagonal No Diagonal Yes No En ESO = mc2 l(l+1)(l+1/2)

2
h i
En
Ĥf0 s = Not Diagonal No Diagonal Yes No En Ef0 s = − 2mc 2
4n
(j+1/2) −3
Ĥr0 + ĤSO
0

ĤZ0 Diagonal Yes Not Diagonal No No En EZ0 = µBext (ml + 2ms )

ĤZ0 = Diagonal Yes Not Diagonal No No En + µBext (ml + 2ms ) Diagonal matrix elements of
Ĥ 0 + ĤZ0 Ĥf0 s in the uncoupled representation
53

2
h i
En 4n
Ĥf0s = Not Diagonal No Diagonal Yes No En + 2mc2
3− (j+1/2) Diagonal matrix elements of
Ĥ 0 + Ĥf0 s ĤZ0 in the coupled representation
7 Finding First Order Energy Corrections for the Intermediate Field Zeeman Effect Con-
tinued
Reconsider the following perturbing Hamiltonian Ĥ 0 = ĤZ0 + Ĥf0 s in the coupled representation (|l, j, mj i)
when Ef0 s ≈ EZ0 .
 
5γ − β 0 0 0 0 0 0 0

 0 5γ + β 0 0 0 0 0 0 


 0 0 γ − 2β 0 0 0 0 0 


 0 0 0 γ + 2β 0 √
0 0 0 

0
Ĥ = −  2 2 (30)
− 3β

 0 0 0 0 γ√ 3 β 0 0 
 
2 1

 0 0 0 0 3 β 5γ − 3 β 0 √
0 

2 2
0 0 0 0 0 0 γ√
+ 3β 3 β
 
 
2
0 0 0 0 0 0 3 β 5γ + 13 β
2 2
in which γ = α8 13.6 eV, α = 4πe0 h̄c , β = µB Bext and the basis states are chosen in the order of |ψ1 i =
|0, 12 , 21 i, |ψ2 i = |0, 12 , − 21 i, |ψ3 i = |1, 23 , 32 i, |ψ4 i = |1, 23 , − 32 i, |ψ5 i = |1, 32 , 12 i, |ψ6 i = |1, 21 , 12 i,
|ψ7 i = |1, 32 , − 12 i, and |ψ8 i = |1, 21 , − 21 i.

21. Explain in words how to find a “good” basis and corrections to the energies for the intermediate field
Zeeman effect (Ef0 s ≈ EZ0 ).

54
OPTIONAL: The final three questions in this tutorial are optional.

22. Determine the first order corrections to the energies for the intermediate field Zeeman effect (Ef0 s ≈ EZ0 )
in which the perturbation Ĥ 0 = ĤZ0 + Ĥf0 s in the coupled representation is given in equation (30).

55
The energy levels for the n = 2 states of the hydrogen atom in the intermediate field Zeeman effect are
given below.

Table 1: Energy Levels in the Intermediate Field Zeeman Effect (n = 2)

1 = E2 − 5γ + β
2 = E2 − 5γ − β
3 = E2 − γ + 2β
4 = E2 − γ − 2β p
5 = E2 − 3γ + β/2 + p4γ 2 + (2/3)γβ + β 2 /4
6 = E2 − 3γ + β/2 − p4γ 2 + (2/3)γβ + β 2 /4
7 = E2 − 3γ − β/2 + p4γ 2 − (2/3)γβ + β 2 /4
8 = E2 − 3γ − β/2 − 4γ 2 − (2/3)γβ + β 2 /4

23. Use the appropriate Taylor series expansion to check that the corrections to the energies in the interme-
diate field Zeeman effect are consistent with the corrections found in the limiting cases of the strong and
weak field Zeeman effects earlier.

56
24. Below is a graph of the splitting of the energy levels of the hydrogen atom for the weak, intermediate, and
strong field Zeeman effect for the n = 2 subspace. Discuss whether the graph is consistent with what you
have learned. Be sure to state whether the number of states is consistent in each regime (weak, strong,
and intermediate field Zeeman effect).

1
Griffiths, David J. Introduction to Quantum Mechanics. 2nd ed. Upper Saddle River, NJ: Pearson Prentice Hall, 2005. pg. 249

57
** Check your answers to questions 21-24. **

21. To find a “good” basis, we must " diagonalize √Ĥ 0 in the#degenerate

" subspace of √
Ĥ 0 . This
# requires diagonal-
2 2 2 2
γ√− 3β 3 β γ√ + 3β 3 β
izing the 2 × 2 block diagonals − 2 1
and − 2
. The “good” basis
3 β 5γ − 3 β 3 β 5γ + 13 β
will be {|ψ1 i, |ψ2 i, |ψ3 i, |ψ4 i, a|ψ5 i+b|ψ6 i, c|ψ5 i+d|ψ6 i, e|ψ7 i+f |ψ8 i, g|ψ7 i+h|ψ8 i}, in which a, b, c, d, e, f, g,
and h are obtained by diagonalizing the block diagonals.
The corrections to the energies in Table 1 are the diagonal matrix elements of Ĥ 0 in the “good” basis.
22.
E10
5γ − β
=
E20 =
5γ + β
E30
γ − 2β
=
E40 =
γ + 2β
E50
p
3γ − β/2 − p4γ 2 + (2/3)γβ + β 2 /4
=
E60
3γ − β/2 + p4γ 2 + (2/3)γβ + β 2 /4
=
E70
3γ + β/2 − p4γ 2 − (2/3)γβ + β 2 /4
=
E80
3γ + β/2 + 4γ 2 − (2/3)γβ + β 2 /4
=
q
23. In the strong field limit (β γ), 4γ 2 ± 23 γβ + 14 β 2 ≈ 12 β ± 23 γ.

E10 = E2 − 5γ + β
E20 = E2 − 5γ − β
E30 = E2 − γ + 2β
E40 = E2 − γ − 2β
E50 = E2 + β − 37 γ
E60 = E2 − 11
3 γ
E70 = 11
E2 − 3 γ
E80 = E2 − β − 37 γ
q
In the weak field limit (γ β), 4γ 2 ± 23 γβ + 41 β 2 ≈ 2γ ± 16 β.

E10 = E2 − 5γ + β
E20 = E2 − 5γ − β
E30 = E2 − γ + 2β
E40 = E2 − γ − 2β
E50 = E2 − γ + 23 β
E60 = E2 − 5γ + 13 β
E70 = E2 − γ − 23 β
E80 = E2 − 5γ − 13 β

24. In the strong field, we found a two-fold degeneracy remaining in the energy spectrum after the two
step approximation. In the weak field, we found no degeneracy remaining in the energy spectrum after the
two step approximation. The results are consistent.

If your answers to questions 21-24 do not match with the checkpoint, go back and reconcile any differences.

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3 Hydrogen Atom DPT Tutorial55

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3 Hydrogen Atom DPT Tutorial55

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Name

Finding Splitting in the Hydrogen Atom Energy Spectrum due

2 Notes for this tutorial:

* We will only consider the bound states of the hydrogen atom.

* The unperturbed bound state energies En are given by En = − 13.6eV

Mass of the electron: m = 9.11 × 10−31 kg

Charge of an electron (magnitude): e = 1.60 × 10−19 C

Speed of light: c = 2.99 × 108 m/s

Permittivity of space: 0 = 8.85 × 10−12 C2 /J m

Bohr magneton: µB = eh̄

En1 = hψn0 |Ĥ 0 |ψn0 i

Ŝ 2 |s ms i = h̄2 s(s + 1)|s ms i Ŝz |s ms i = h̄ms |s ms i

L̂2 |l ml i = h̄2 l(l + 1)|l ml i L̂z |l ml i = h̄ml |l ml i

Jˆ2 |l, s, j, mj i = h̄2 j(j + 1)|l, s, j, mj i Jˆz |l, s, j mj i = h̄mj |l, s, j, mj i

Ŝ 2 |l, s, j, mj i = h̄2 s(s + 1)|l, s, j, mj i L̂2 |l, s, j mj i = h̄2 l(l + 1)|l, s, j, mj i

~ = 1 (Jˆ2 − Ŝ 2 − L̂2 ) = 1 (L̂+ Ŝ− + L̂− Ŝ+ ) + L̂z Ŝz

1. Identify the unperturbed Hamiltonian Ĥ 0 and the perturbing Hamiltonian Ĥ 0 .

5 The Hydrogen Atom Placed in an External Magnetic Field

and combining the relativistic and spin-orbit terms

– Ĥ 0 (spherically symmetric with energy only depending on n as En = − 13.6n2

Ĥ 0 = Ĥf0 s + ĤZ0 (2)

Explain why you agree or disagree with each student.

** Check your answers to question 1. **

Consider the following statement regarding evaluating p̂2 |ψn i.

with Bohr radius

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

Do you agree with Student 2 or Student 3? Explain.

and the radial part is  

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

Explain why you agree or disagree with each student.

l s j Ef0 s Number of States

• For the entire fine structure perturbation Ĥ 0 = Ĥr0 + ĤSO

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

Ĥf0 s = Not Diagonal No Diagonal Yes No Ef0 s = − 2mc 2

Explain why you agree or disagree with each student.

EZ0 = µB Bext (ml + 2ms ) (16)

• ĤZ0 is diagonal in each degenerate subspace of Ĥ0 in the uncoupled representation.

Ĥ 0 Diagonal — Diagonal — — En = − 13.6eV

ĤZ0 Diagonal Yes Not Diagonal No No EZ0 = µBext (ml + 2ms )

Determining a “GOOD” Angular Basis and Corrections to the Energies due to

EZ0  Ef0 s Ef0 s ≈ EZ0 Ef0 s  EZ0

Strong Field Intermediate Field Weak Field

Explain why you agree or disagree with Student 2 or Student 3.

Do you agree with Student 2? Explain.

Coupled Representation Uncoupled Representation

|l, j, mj i |l, ml i|s, ms i

Explain why you agree or disagree with each student.

Explain why you agree or disagree with each student.

Determining a “GOOD” Angular Basis and Corrections to the Energies due to

EZ0  Ef0 s Ef0 s ≈ EZ0 Ef0 s  EZ0

Strong Field Intermediate Field Weak Field

Neither the coupled nor the

Choose either the coupled or the

Diagonalize Ĥ 0 = Ĥf0 s + ĤZ0

In the “good” basis, the diagonal matrix

Explain why you agree or disagree with each student.

• Summary of Two-Step Approximation

Explain why you agree or disagree with each student.

– CASE 2: Strong Field Zeeman Effect (EZ0  Ef0 s )

Explain why you agree or disagree with each student.

Explain why you agree or disagree with each student.

Explain why you agree or disagree with each student.

Explain why you agree or disagree with each student.

(−13.6 eV)α2 (−13.6 eV)α2

(−13.6 eV)α2 (−13.6 eV)α2

(−13.6 eV)α2 (−13.6 eV)α2

(−13.6 eV)α2 (−13.6 eV)α2

EZ0  Ef0 s Ef0 s ≈ EZ0 Ef0 s  EZ0

Strong Field Intermediate Field Weak Field

Neither the coupled nor the

Choose either the coupled or the

STEP 2: Consider Ĥ 0 = Ĥf0 s as Diagonalize Ĥ 0 = Ĥf0 s + ĤZ0 in

The uncoupled representation

In the uncoupled representation, the

Explain why you agree or disagree with each student.

Explain why you agree or disagree with each student.

Permittivity of space: 0 = 8.85 × 10−12 C2 /J m

Check your answers to question 1.

and the radial part is

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

– CASE 2: Strong Field Zeeman Effect (EZ0 Ef0 s )

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

EZ0 Ef0 s Ef0 s ≈ EZ0 Ef0 s EZ0

• Strong Field Zeeman Effect (EZ0 Ef0 s )

• Weak Field Zeeman Effect (Ef0 s EZ0 )