Notes 4: The Zeeman Effect

Pieter Zeeman in 1896 discovered that a magnetic field broadened the yellow D lines produced
when sodium is placed in a flame. Later this broadening was shown to be a splitting of the spectral lines
into as many as 15 components. The line splitting results from the effect of the magnetic field on the
atomic energy levels. In 1897, Thomas Preston reported a similar effect to Zeeman but with more
complicated results. This ‘anomalous Zeeman effect’ is now known to be due to half-integer total electron
spin.
The Zeeman effect is very useful in measuring the strengths of stellar magnetic fields.

Hamiltonian for a charge in electric and magnetic fields

The Hamiltonian for the hydrogen atom was found by adding the electrostatic potential energy operator to
the kinetic energy operator. Because the Lorentz force does no work, it does not have a scalar potential
energy. In classical Lagrangian mechanics, the velocity-dependent Lorentz force is accounted for by
using a velocity-dependent potential, U = −qA ⋅ v, where A is the vector potential related to the
magnetic field by B = ∇ × A. The quantization of the classical Hamiltonian for a charged particle in
electric and magnetic fields leads to the Schrödinger equation

∂ψ  1
=  ( p − qA ) + qϕ ψ ,
2
i (4.1)
∂t  2 M 

where ϕ is the scalar potential and

p =−i∇. (4.2)

For a uniform magnetic field, B0, the vector potential can be taken to be

1
A (r ) =
− r × B0 . (4.3)
2

Note that ∇ ⋅ A = 0. The Hamiltonian in equation (4.1) is such that

 1
Hψ=  ( p − qA ) + qϕ ψ
2

 2M 
1
= ( −i∇ − qA ) ⋅ ( −i∇ψ − qAψ ) + qϕψ (4.4)
2M
2 2 iq q2
=− ∇ψ + ( A ⋅∇ )ψ + A ⋅ Aψ + qϕψ .
2M M 2M
Using vector identities, it can be shown for the vector potential in equation (4.3) that

1
 1
A ⋅ A = ( r ⋅ r )( B 0 ⋅ B 0 ) − ( r ⋅ B 0 )( r ⋅ B 0 )  ,
4
(4.5)
i q q q q
( A ⋅∇ )ψ =× ( r B0 ⋅ p )ψ = − B 0 ⋅ ( r × p )ψ =
− B 0 ⋅ Lψ ,
M 2M 2M 2M
where L is the angular momentum operator. The Hamiltonian for a charged particle in a uniform
magnetic field is then
p2 q q2
H= − B0 ⋅ L + ( r ⋅ r )( B 0 ⋅ B 0 ) − ( r ⋅ B 0 )( r ⋅ B 0 )  + qϕ .
8M 
(4.6)
2M 2M

Application to the Zeeman Effect in hydrogen

Since the electron has a magnetic moment, an additional term has to be added to the Hamiltonian in
equation (4.6). The ‘perturbation’ due to the magnetic field is then
e e2
H =
1
B 0 ⋅ ( L + g eS ) + ( r ⋅ r )( B 0 ⋅ B 0 ) − ( r ⋅ B 0 )( r ⋅ B 0 )  ,
8M 
(4.7)
2M
where g e ≈ 2 is the electron gyromagnetic ratio factor.
It is instructive to consider the relative magnitudes of the terms that are linear and quadratic in the
magnetic field. Suppose the hydrogen atom is in its ground state. Then the ratio of the quadratic term to
the linear term is roughly
eB0 a0 2
, (4.8)


=
where a0 4πε 0  2 ( Me
= )2
0.529 ×10−10 m is the Bohr radius. The two terms will be roughly equal at
field strength


=
Beq = 2
2.35 ×105 T. (4.9)
ea0

This is much larger than the strongest magnetic fields produced on Earth by explosive field compression
(~3000 T) but much less than the fields associated with magnetars (highly magnetic neutron stars), which
can be as large as 1011 T.
When B0 = Beq, the energy corresponding the magnetic perturbation to the Hamiltonian is

eBeq  2
~ = = 2I p , (4.10)
M Ma0 2

where Ip is the ionization potential of hydrogen. Hence, at even the strongest ‘terrestrial’ fields, the
magnetic effects can be treated as a perturbation.
The hydrogen atom’s internal magnetic field due to ‘orbital’ motion of the electron (see equation
3.21) will be comparable to the external magnetic field when

2
 1 e
B0 ≈ α 2 Beq 12.5 T.
=≈ (4.11)
4πε 0 Mc a0
2 3

The weak-field Zeeman effect

From equation (4.11), we see that line splitting due to fine structure will be larger than the Zeeman effect
if B0  α 2 Beq . The Zeeman effect in this weak-field case is treated by including the fine structure terms
in the unperturbed Hamiltonian and using as the perturbation to the Hamiltonian

e
=
H 1
B 0 ⋅ ( L + g eS ) . (4.12)
2M

The operators J2 and Jz commute with the fine structure Hamiltonian. They will commute with the
Zeeman perturbation provided we choose the z-axis parallel to the external magnetic field, so that

e
=H1 B0 ( Lz + g e S z ) . (4.13)
2M

The good states theorem tells us we can use non-degenerate perturbation theory with n l j m j as the
good states. To find the first order corrections to the energies, we need to find

L + g eS = J + ( g e − 1) S . (4.14)

Since J is constant, L and S are constrained to be coplanar with J, as shown in the figure below.

Since the azimuthal angle of the plane relative to the direction of J is uniformly distributed, the
expectation value of S is equal to its projection onto J, i.e.

S⋅J
S = J
J2

We can evaluate S ⋅ J by noting L = J – S so that

L2 = J 2 − 2S ⋅ J + S 2 .

3
Hence

J 2 − L2 + S 2  2
=
S⋅J =  j ( j + 1) − l ( l + 1) + s ( s + 1)  .
2 2 

It follows that

 S⋅J
L + g eS = 1 + ( g e − 1) 2  J = g J J .
 J 

where

g e − 1 j ( j + 1) − l ( l + 1) + s ( s + 1)
gJ = 1+ (4.15)
2 j ( j + 1)

is called the Landé g-factor.

The corrections to the energies are

e
=E1 = B0 g J m j µ B B0 g J m j ,
2M

where

e
µB
= T −1 5.788 ×10−5 eV T −1 ,
= 9.274 ×10−24 J =
2M

is called the Bohr magneton.

The Zeeman effect splits the n = 1, l = 0, j = ½ ground state of hydrogen in two, since mj = ±1/2.
Since gJ = 1, the Zeeman contribution to the energy is ± µ B B0 .

Problem 7.24 Consider the eight n = 2 states. Find the energy of each state under weak Zeeman splitting
and construct a diagram to show how the energies evolve as B0 increases. Label each line clearly and
indicate it slope.
Solution: The table shows the relevant quantum numbers, the Landé g-factor, the energy for zero external
field and the derivative of the energy with respect to field strength for all eight states.

l j mj gJ Efs (eV) dE/dB0 (eV T-1)

0 1/2 1/2 1 -3.397556534 2.894 10-5
0 1/2 -1/2 1 -3.397556534 -2.894 10-5
1 1/2 1/2 -1/3 -3.397556534 -9.647 10-6
1 1/2 -1/2 -1/3 -3.397556534 9.647 10-6
1 3/2 3/2 4/3 -3.397511307 1.158 10-4
1 3/2 1/2 4/3 -3.397511307 3.859 10-5
1 3/2 -1/2 4/3 -3.397511307 -3.859 10-5
1 3/2 -3/2 4/3 -3.397511307 -1.158 10-4

4
How the energies evolve with field strength are shown below. The blue lines are for the l = 0 states and
the red lines for the j = 3/2 states.
-3.397
mj = 3/2

mj = 1/2
E (eV)

mj = 1/2

j = 3/2 mj = -1/2
j = 1/2
mj = 1/2
mj = -1/2
mj = -1/2

mj = -3/2
-3.398
0 1 2 3 4
B0 (T)

The strong-field Zeeman effect

For the strong field Zeeman effect, fine structure is treated as a perturbation to a Hamiltonian that
includes the interaction with the external magnetic field.
Since ml and ms are quantum numbers for the unperturbed wave function, the Zeeman effect contribution
to the energy is

e
EZ= B0 ( ml + g e ms =
) µ B B0 ( ml + ge ms ) . (4.16)
2M

Even though the degeneracies in ml and ms have been lifted by the external magnetic field, the eigenstates
of the unperturbed Hamiltonian are degenerate because their energies do not depend on the angular
momentum quantum number, l. However, both H0 and the fine structure perturbation H1 commute with
the operator L2, which can serve as the Hermitian operator A in the good states theorem. The eigenstates
n l ml ms are good states and can be used in non-degenerate perturbation theory to find the fine structure
corrections to the energies. (Note since ge is not exactly equal to 2 and is an irrational number, there is no
other degeneracy, contrary to what is stated in the textbook.) The relativistic correction is the same as in
the zero external field case. For spin-orbit coupling

5
 e2 1
1
H SOC ( ge − 1)
= S ⋅ L, (4.17)
8πε 0 M c r
2 2 3

we need

S ⋅ L= n l ml ms S ⋅ L n l ml m=
s S x Lx + S y Ly + S z Lz
(4.18)
= Sx Lx + S y Ly + S z Lz .

Noting 1 that =
Lx =
Ly 0 for eigenstates of Lz, we get

S=
⋅L Sz =
Lz  2 ms ml . (4.19)

Putting the pieces together, we get

e2 1
1
ESOC ( ge − 1)
= r −3 S ⋅ L
8πε 0 M 2 c 2
(4.20)
e2 1 2
= ( ge − 1)  ms ml
2

8πε 0 M 2 c 2 n3l ( l + 1)( 2l + 1) a 3

Setting ge = 2, on adding the relativistic correction, we get the fine structure contribution to be

α2 3  l ( l + 1) − ml ms  
=E1fs En0  − 2n    . (4.21)
n 2 4
  l ( l + 1)( 2l + 1) 

For l = 0, the term in the square brackets is indeterminate. It can be shown that for l = 0,

α2 3 
=E1fs En0  − n  . (4.22)
4 
2
n

Problem 7.27 Consider the eight n = 2 states. Find the energy of each state under strong-field Zeeman
splitting. Express each answer as the sum of three terms: The Bohr energy, the fine structure contribution
and the Zeeman contribution. If you ignore fine structure altogether, how many distinct levels are there
and what are their degeneracies?
Solution: Let’s use E10 ≈ 13.6 eV as the energy unit. The Bohr energy is then -0.25. The Zeeman energy
in this unit is

1
This can be verified by using equations (4.127), (4.128) and (4.129).

6
 µ B B0 B0
EZ = 0
( ml + ge ms ) = ( ml + ge ms )
E 1
Beq

and the fine structure contribution is

3  l ( l + 1) − ml ms 
2  − 2n   , l > 0,
α 4  l ( l + 1)( 2l + 1) 
E fs = 4 
1

n  3
 − n, l= 0.
4

The table below shows the size of the three contributions to the energy for the n = 2 states assuming that
B0 = 0.01 Beq.
n l ml ms Bohr Zeeman fine structure
2 0 0 1/2 -0.25 0.01 -4.162 10-6
2 0 0 -1/2 -0.25 -0.01 -4.162 10-6
2 1 1 1/2 -0.25 0.02 -8.325 10-7
2 1 0 1/2 -0.25 0.01 -1.942 10-6
2 1 -1 1/2 -0.25 0.01πα2 = 1.674 10-6 -3.052 10-6
2 -6
2 1 1 -1/2 -0.25 -0.01πα = -1.674 10 -3.052 10-6
2 1 0 -1/2 -0.25 -0.01 -1.942 10-6
2 1 -1 -1/2 -0.25 -0.02 -8.325 10-7

If we ignore fine structure altogether and take ge =2, there are 5 levels corresponding to Zeeman terms -
0.02, -0.01, 0.0, 0.01 and 0.02. The degeneracy is 2 except for the non-degenerate -0.02 and 0.02 levels.

The intermediate-field Zeeman effect

For n > 1, note that it is not straightforward to connect the states used for the strong-field Zeeman effect
to the states used for the weak-field Zeeman effect because different sets of quantum numbers were used
to specified the unperturbed states 2. To make the connection, we need to consider the intermediate field
Zeeman effect in which the Zeeman and fine structure perturbation are treated together as a perturbation.
The perturbation to the Hamiltonian is

=
H 1
H 1fs + H Z1 . (4.23)

Since there are no obvious good states that work simultaneously for both terms, degenerate perturbation
has to be used. Because H Z1 is simpler than H 1fs , the calculation of the elements of the W matrix are

simpler if the basis states are chosen to be n l j m j . We then need to calculate n l j m j ml n l j m j

and n l j m j ms n l j m j . These expectation values can be evaluated by writing n l j m j as a linear

2
For n = 1 the weak- and strong-field formulae give the same energies.

7
combination of eigenstates n l s ml ms . This involves the Clebsch-Gordan coefficients (see section 4.4.3
of GS). Since addition of angular momentum does not involve the principal quantum number, we drop the
dependence on n. The required relationships are then

j mj = ∑
m=j ml + ms
Cmlsjl ms m j l s ml ms . (4.24)

For l = 0, the two eigenstates are

11 1 1
ψ1
= = 0 0 ,
22 2 2
(4.25)
1 −1 1 −1
ψ2
= = 0 0 .
2 2 2 2

The one-to-one correspondence between angular moment states explains why the weak- and strong-field
formulae give the same energy for the n = 1 states.
For l = 1, the six eigenstates are

3 3 1 1
ψ3
= = 1 1 ,
2 2 2 2
3 −3 1 −1
ψ4
= = 1 −1 ,
2 2 2 2
3 1 2 1 1 1 1 −1
ψ5
= = 1 0 + 1 1 ,
2 2 3 2 2 3 2 2
(4.26)
1 1 1 1 1 2 1 −1
ψ6 = =
− 1 0 + 1 1 ,
2 2 3 2 2 3 2 2
3 −1 2 1 −1 1 1 1
ψ7 = = 1 0 + 1 −1 ,
2 2 3 2 2 3 2 2
1 −1 1 1 −1 2 1 −1
ψ8 = = 1 0 − 1 −1 .
2 2 3 2 2 3 2 2

We then have that the Zeeman contribution to the W matrix is (taking ge = 2)

8
 WZ ,=
ij µ B B0 ψ i ( ml + g e ms )ψ j ⇒
1 0 0 0 0 0 
0 0
 
0 −1 0 0 0 0 0
 0
0 0 2 0 0 0 
0 0
 
0 0 0 −2 0 0 0 0  (4.27)
WZ = µ B B0 
0 
.
0 0 0 0 23 − 2 3 0
 
0 0 0 0 − 2 3 13 0 0 
 
0 0 0 0 0 0 −2 3 − 2 3 
 
0 0 0 0 0 0 − 2 3 −1 3 

Since n l j m j is a good state for H 1fs , the fine structure contribution gives a diagonal matrix with
values given by equation (3.33),

 −5 0 0 0 0 0 0 0
 
0 −5 0 0 0 0 0 0
0 0 −1 0 0 0 0 0
 
α2 0  0 0 0 −1 0 0 0 0
W fs = E1 . (4.28)
64 0 0 0 0 −1 0 0 0
 
0 0 0 0 0 −5 0 0
0 0 0 0 0 0 −1 0
 
0 0 0 0 0 0 0 −5 

Looking at the structure of the resultant W matrix, we see that the top left 4×4 matrix is diagonal and the
bottom right 4×4 matrix is block diagonal and consists of two 2×2 matrices. Thus it is easy to determine
the perturbations to the energy for 4 states and the other 4 energy perturbations can be found by
diagonalization of 2×2 matrices. Let’s consider the bottom 2×2 matrix,

 2 2 
 −γ − β − β 
3 3
W78 =  , (4.29)
 2 1 
 − β −5γ − β 
 3 3 

where γ = α 2 E10 64 and β = µ B B0 .

From equation (2.9), we find the energy corrections are

9
 2

( −6γ − β ) ±  4γ − β  + β 2
1 8
 3  9 1 2 β2
E±1 = =−3γ − β ± 4γ 2 − γβ + . (4.30)
2 2 3 4

In the weak-field limit β → 0 and the strong-field limit γ → 0, the energies are E±1 = ( −3 ± 2 ) γ and

 1 1
E±1 = − ±  β , respectively. The matrix W78 becomes in these limits
 2 2

 2 2
 − − 
 −1 0   3 3 
=lim W78 γ=
  , lim W78 β . (4.31)
β →0
 0 −5  γ →0  2 1 
− − 
 3 3 

3 −1 1 −1
In the limit of zero field the states ψ 7 = and ψ 8 = are eigenfunctions. In the limit of a
2 2 2 2
very strong field, the eigenvectors of W 78 are

1  1  1  2
 ,  , (4.32)
3 − 2 3 1 

which correspond to eigenfunctions

1 2 1 −1
ψ 7 − ψ 8 =1 −1 ,
3 3 2 2
(4.33)
2 1 1 −1
ψ7 + ψ8 =
1 0 .
3 3 2 2

We conclude that as the external magnetic field increases in strength the good states evolve from
n l j m j to n l s ml ms , and that the intermediate-field Zeeman effect has limits that are consistent
with the weak- and strong-field Zeeman effects.

10