Topic 3 QP2:

Fine structure of hydrogen

 Outline
Hamiltonian of hydrogen-like atoms in QM

Degeneracy of energy levels of bound states

Relativistic corrections, partial lifting of

degeneracy

Calculation of first-order shift of energy levels

Side-remarks: proton radius

 Hamiltonian of hydrogen-like atoms

0 ~2 ⇤ 2 Ze2
H = r
2m 4⇥ 0 r

The leading relativistic corrections are:

0 p⌅ 4 1 1 dV ⌅ ⌅ ⇤~2 Ze2
H = 3 2
+ 2 2
L·S+ 2 2
(⌅r)
8m c 2m c r dr 2m c 4⇤⇥0

H’ can be derived from

the Dirac equation [1928]
 Hamiltonian of hydrogen-like atoms

0 p⌅ 4 1 1 dV ⌅ ⌅ ⇤~2 Ze2
H = 3 2
+ 2 2
L·S+ 2 2
(⌅r)
8m c 2m c r dr 2m c 4⇤⇥0

H’ must be treated as a perturbation

H’ has less symmetry than H0 → partial lifting of degeneracy:

the fine structure splitting of energy levels of hydrogen

Despite the large degeneracy of the unperturbed energy levels,

one can use nondegenerate perturbation theory if one uses the
right basis (find operators that commute with H, i.e. a C.S.C.O.)
Non-relativistic Hamiltonian of hydrogen-like atoms

0 ~2 ⇤ 2 Ze2 mc2 (Z )2
H = r En0 =
2m 4⇥ 0 r 2 n2
e2 1
= ⇡
4⇥⇤0 ~c 137

C.S.C.O.: H0, L2, S2, Lz, Sz or H0, L2, S2, J2, Jz

Spin does not play a role, it does not affect the energy

The states have labels that correspond to distinct eigenvalues

of a C.S.C.O.

⇤nlm (r, , ⇥) = Rnl (r)Ylm ( , ⇥)

Energy levels are independent of s,ms, but also of l,m

 Degeneracy of energy levels

[H,L±]=0 implies: energy levels are independent of m

⇤l, m + 1|[L+ , H]|l, m⌅ = 0 ⇤l, m|H|l, m⌅ = ⇤l, m + 1|H|l, m + 1⌅ ⇥m

Energy levels are also independent of l quantum number

This l independence does not follow from [H,L2]=0

It is specific to the Coulomb potential

n
X1
2
Degeneracy per n: 2 (2l + 1) = 2n
l=0
 Perturbation of energy levels
4 2 2
0 p⌅ 1 1 dV ⌅ ⌅ ⇤~ Ze
H = 3 2
+ 2 2
L·S+ 2 2
(⌅r)
8m c 2m c r dr 2m c 4⇤⇥0

Spin now plays a role, it will affect the energy

The z-component of the orbital angular momentum and spin not

separately conserved: perform addition of angular momentum!

H0+H’, L2, S2, Lz, Sz does not form a C.S.C.O.

C.S.C.O.: H0+H’, L2, S2, J2, Jz

This C.S.C.O. allows one to use nondegenerate perturbation

theory, despite the large 2n2 degeneracy of the unperturbed levels
 Fine structure of hydrogen-like atoms

4 2 2
0 p⌅ 1 1 dV ⌅ ⌅ ⇤~ Ze
H = 3 2
+ 2 2
L·S+ 2 2
(⌅r)
8m c 2m c r dr 2m c 4⇤⇥0

Energy levels will not only depend on n, but also on j

2
✓ ◆
1 0 0 (Z ) n 3
Enj = ⇥nlsjmj |H |nlsjmj ⇤ = En 1
n2 j+2 4

Remaining degeneracy: l=j±½ (and all mj values per j)

The energies of the 2s½ and 2p½ are thus the same

Spectroscopic notation: nlj or n(2s+1)lj

 Magnitude of fine splitting

 2
✓ ◆
0+1 0 (Z ) n 3
Enj = En 1+ 1
n2 j+ 2
4

Estimate of the magnitude of the fine splitting for Z=1:

2
↵ 13.6 eV 1 1
E2p 32 E2p 12 = E20 (1 2) = ⇡ 4.5 · 10 5
eV
4 4 1372 4

14 1 19
1 eV = 2.41797 · 10 Hz = 8065.48 cm = 1.60218 · 10 J
5
4.5 · 10 eV 10.9 GHz

Visible light (400-800 nm) is a few eV (~3-1.5 eV)

 Hints for the calculation

0 p4 1 0 2
H1 = = (H V)
8m3 c2 2mc2
2
(Z )
Try to write everything a.s.a.p. with pre-factor En0
n2

Sum the three contributions for the following cases separately:

l=0
1
j =l+ l 6= 0
2
1
j=l l 6= 0
2
 Background info
Lamb shift

H’: The energies of the 2s½ and 2p½ are equal

In reality, they are not the same: Lamb shift

1
(E2s 12 E2p 12 ) ⇡ (E2p 32 E2p 12 )
10
Lamb shift: 1058 MHz (4⋅10-6 eV)

Willis E. Lamb Jr (1913–2008)

Calculation of the Lamb shift requires Quantum

Electrodynamics (QED) [beyond the scope of this course]
 Origin of the relativistic corrections

0 p⌅ 4 1 1 dV ⌅ ⌅ ⇤~2 Ze2
H = 3 2
+ 2 2
L·S+ 2 2
(⌅r)
8m c 2m c r dr 2m c 4⇤⇥0
p p 2
p4
Kinematical term: p 2 c2 + m2 c4 mc2 ⇡ 3 2
+ ...
2m 8m c
Spin-orbit coupling: coupling of electron’s magnetic moment (∝ spin)
to internal magnetic field due to proton charge

Darwin term: uncertainty in r of V(r) ≠ V(r+Δr) Background info

hV (r + r) V (r)i ⇠ h( r)2 r 2 V i
~ 2
⇥ 2 V ⇠ (⇥r)
( r)2 ⇠ 2 2 r
m c
This assumes a point charge, but the proton has a size
 Background info
Effect of the finite proton radius
Proton has charge distribution ρ with finite extent: deviation from Coulomb
Z ✓ ◆
2 Ze
E ⇥ e d⇧r |⇤(r)| V (r)
4 ⌅0 r
Z
e ⇧ 2 V (r)
⇤ |⇤(0)|2 d⇧r r2 ⌃
6
✓ Z ◆
e 2 2
⇤ |⇤(0)| ⌅r ⇧ d⇧r⇥(r)
6
✓ ◆3
Ze2 2 2 2 1 Zm
= |⇤(0)| ⌅r ⇧ |⇤(0)| =
6 ⇥ n
p
rp = hr2 i
proton

rp = 0.8751(61) fm [CODATA, 2014]

rp = 0.897(18) fm [electron-proton scattering]
 Effect of the proton spin

The proton spin interacts with the electron spin: hyperfine structure
Topic of the next lecture
Large Z atoms Background info
An expression for Enj that is valid to all orders in α can be derived
(see problem 6.19 of the book)

However, for Zα ≥ 1 problems arise: complex energies signal unstable

states: supercritical atoms (different from radioactive unstable atoms)
Taking into account the finite size of the proton: Z ≥ 175 (> 1/α)

Largest Z atom produced in

the lab: Z=118

As of 2015, all elements up to

Z=118 have been recognized
 What you have to know

Section 6.3 of the book: fine structure of hydrogen

C.S.C.O.’s of H0 and H’, degeneracy

order of magnitude of fine splitting and Lamb shift

ingredients of the perturbative calculation