Lectures 7-8: Fine and hyperfine structure of hydrogen

o Fine structure

o Spin-orbit interaction.

o Relativistic kinetic energy correction

o Hyperfine structure

o The Lamb shift.

o Nuclear moments.

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 Spin-orbit coupling in H-atom

o Fine structure of H-atom is due to spin-orbit interaction:

Jˆ is a max
Zh ˆ ˆ
ΔE so = α S⋅L
2m 2cr 3 Lˆ
Sˆ
o If L is parallel to S => J is a maximum => high energy €
configuration. +Ze
€ € -e
€
o Angular momenta are described in terms of quantum
numbers, s, l and j:
Jˆ is a min
Jˆ = Lˆ + Sˆ
Lˆ
Jˆ 2 = (Lˆ + Sˆ )(Lˆ + Sˆ ) = Lˆ Lˆ + SˆSˆ + 2 Sˆ ⋅ Lˆ
1 €
Sˆ ⋅ Lˆ = (Jˆ ⋅ Jˆ − Lˆ ⋅ Lˆ − Sˆ ⋅ Sˆ ) +Ze
2
h2
€ -e
ˆ ˆ
=> S ⋅ L = [ j( j + 1) − l(l + 1) − s(s + 1)]
2 Sˆ
Zh 3 1
∴ΔE so = α [ j( j + 1) − l(l +1) − s(s + 1)]
4m 2c r 3
€ €
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 Spin-orbit effects in H fine structure

o For practical purposes, convenient to express spin-orbit coupling as

a
ΔE so = [ j ( j + 1) − l(l + 1) − s( s + 1)]
2
2 2 2 3
where a = Ze μ 0 h /8πm r is the spin-orbit coupling constant. Therefore, for the 2p
electron:
€ ΔE = a ⎡3 ⎛ 3 + 1⎞ −1(1+ 1) − 1 ⎛1 + 1⎞⎤ = + 1 a
so ⎢ ⎜ ⎟ ⎜ ⎟⎥
€ 2 ⎣ 2 ⎝ 2 ⎠ 2 ⎝ 2 ⎠⎦ 2
a ⎡1 ⎛1 ⎞ 1 ⎛1 ⎞⎤
ΔE so = ⎢ ⎜ + 1⎟ −1(1+ 1) − ⎜ + 1⎟⎥ = −a
2 ⎣2 ⎝2 ⎠ 2 ⎝2 ⎠⎦

j = 3/2 +1/2a
€E
2p1 Angular momenta aligned

j = 1/2 -a
Angular momenta opposite
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 Spin-orbit coupling in H-atom

o The spin-orbit coupling constant is directly measurable from the doublet structure
of spectra.

o If we use the radius rn of the nth Bohr radius as a rough approximation for r (from
Lectures 1-2): n 2h2
r = 4πε 0
mZe 2
Z4
=> a ~ 6
n
o Spin-orbit coupling increases sharply with Z. Difficult for observed for H-atom, as
Z = 1: 0.14 Å (H), 0.08 Å (H), 0.07 Å (H).
€
Z4
o Evaluating the quantum mechanical form, a~ 3
n [ l(l + 1)(2l + 1)]

o Therefore, using this and s = 1/2: Z 2α 4 2 [ j( j + 1) − l(l + 1) − 3/4]

ΔE so = mc
€ 2n 3 l(l + 1)(2l + 1)

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 Term Symbols

o Convenient to introduce shorthand notation to label energy levels that occurs in the LS
coupling regime.

o Each level is labeled by L, S and J: 2S+1 LJ

o L = 0 => S
o L = 1 => P
o L = 2 =>D
o L = 3 =>F

o If S = 1/2, L =1 => J = 3/2 or 1/2. This gives rise to two energy levels or terms, 2P3/2 and 2P1/2

o 2S + 1 is the multiplicity. Indicates the degeneracy of the level due to spin.

o If S = 0 => multiplicity is 1: singlet term.
o If S = 1/2 => multiplicity is 2: doublet term.
o If S = 1 => multiplicity is 3: triplet term.

o Most useful when dealing with multi-electron atoms.

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 Term diagram for H fine structure

o The energy level diagram can also be drawn as a term diagram.

o Each term is evaluated using: 2S+1LJ

o For H, the levels of the 2P term arising from spin-orbit coupling are given below:

+1/2a
P3/2
2
E Angular momenta aligned
2p1 (2P)

-a
2
P1/2 Angular momenta opposite

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 Hydrogen fine structure

o Spectral lines of H found to be composed of

closely spaced doublets. Splitting is due to
interactions between electron spin S and the
orbital angular momentum L => spin-orbit
coupling.

o H line is single line according to the Bohr or

Schrödinger theory. Occurs at 656.47 nm for
H and 656.29 nm for D (isotope shift, ~0.2
H
nm).

o Spin-orbit coupling produces fine-structure

splitting of ~0.016 nm. Corresponds to an
internal magnetic field on the electron of about
0.4 Tesla.

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 Relativistic kinetic energy correction

o According to special relativity, the kinetic energy of an electron of mass m and velocity v is:
p2 p4
T≈ −
2m 8m 3c 2
o The first term is the standard non-relativistic expression for kinetic energy. The second term is
the lowest-order relativistic correction to this energy.
€
o Using perturbation theory, it can be show that

Z 2α 4 ⎛ 1 3⎞
ΔE rel = − 3 mc 2 ⎜ − ⎟
n ⎝2l +1 8n ⎠
o Produces an energy shift comparable to spin-orbit effect.

o A complete relativistic €
treatment of the electron involves the solving the Dirac equation.

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 Total fine structure correction

o For H-atom, the spin-orbit and relativistic corrections are comparable in magnitude, but much
smaller than the gross structure.

Enlj = En + EFS

o Gross structure determined by En from Schrödinger equation. The fine structure is determined
by
Z 4α 4 2⎛ 1 3⎞
ΔE FS = ΔE so + ΔE rel = − mc ⎜ − ⎟
2n 3 ⎝2l + 1 8n ⎠

o As En = -Z2E0/n2, where E0 = 1/22mc2, we can write

€ Z 2 E 0 ⎛ Z 2α 2 ⎛ 1 3 ⎞⎞
E H −atom = − 2 ⎜1+ ⎜ − ⎟⎟
n ⎝ n ⎝ j + 1/2 4n ⎠⎠

o Gives the energy of the gross and fine structure of the hydrogen atom.
€

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 Fine structure of hydrogen

o Energy correction only depends on j, which is

of the order of 2 ~ 10-4 times smaller that the
principle energy splitting.

o All levels are shifted down from the Bohr

energies.

o For every n>1 and l, there are two states

corresponding to j = l ± 1/2.

o States with same n and j but different l, have

the same energies (does not hold when Lamb
shift is included). i.e., are degenerate.

o Using incorrect assumptions, this fine structure

was derived by Sommerfeld by modifying Bohr
theory => right results, but wrong physics!

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 Hyperfine structure: Lamb shift

o Spectral lines give information on nucleus. Main effects are isotope shift and hyperfine
structure.

o According to Schrödinger and Dirac theory, states with same n and j but different l are
degenerate. However, Lamb and Retherford showed in 1947 that 2 2S1/2 (n = 2, l = 0, j = 1/2)
and 22P1/2 (n = 2, l = 1, j = 1/2) of H-atom are not degenerate.

o Experiment proved that even states with the same total angular momentum J are energetically
different.

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 Hyperfine structure: Lamb shift

1. Excite H-atoms to 22S1/2 metastable state by e- bombardment. Forbidden to spontaneuosly

decay to 12S1/2 optically.

2. Cause transitions to 22P1/2 state using tunable microwaves. Transitions only occur when
microwaves tuned to transition frequency. These atoms then decay emitting Ly line.

3. Measure number of atoms in 2 2S1/2 state from H-atom collisions with tungsten (W) target.
When excitation to 22P1/2, current drops.

4. Excited H atoms (22S1/2 metastable state) cause secondary electron emission and current from
the target. Dexcited H atoms (12S1/2 ground state) do not.

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 Hyperfine structure: Lamb shift

o According to Dirac and Schrödinger theory, states with the same n and j quantum
numbers but different l quantum numbers ought to be degenerate. Lamb and
Retherford showed that 2 S1/2 (n=2, l=0, j=1/2) and 2P1/2 (n=2, l=1, j=1/2) states of
hydrogen atom were not degenerate, but that the S state had slightly higher energy
by E/h = 1057.864 MHz.

o Effect is explained by the theory of quantum electrodynamics, in which the

electromagnetic interaction itself is quantized.

o For further info, see http://www.pha.jhu.edu/~rt19/hydro/node8.html

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 Hyperfine structure: Nuclear moments

o Hyperfine structure results from magnetic interaction between the electron’s total
angular momentum (J) and the nuclear spin (I).

o Angular momentum of electron creates a magnetic field at the nucleus which is

proportional to J.

ˆ ˆ ˆ
o Interaction energy is therefore ΔE hyperfine = −μˆ nucleus ⋅ Belectron ∝ I ⋅ J

o Magnitude is very small as nuclear dipole is ~2000 smaller than electron ( ~1/m).
€
o Hyperfine splitting is about three orders of magnitude smaller than splitting due to
fine structure.

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 Hyperfine structure: Nuclear moments

o Like electron, the proton has a spin angular momentum and an associated intrinsic dipole
moment e ˆ
μˆ p = g p I
M
o The proton dipole moment is weaker than the electron dipole moment by M/m ~ 2000 and
hence the effect is small.
gpe 2
o € be shown to be:
Resulting energy correction can ΔE p = 2 3
Iˆ ⋅ Jˆ
mMc r

o Total angular momentum including nuclear spin, orbital angular momentum and electron spin
is
Fˆ = Iˆ + Jˆ €
where F = f ( f + 1)h
Fz = m f h
o €The quantum number f has possible values f = j + 1/2, j - 1/2 since the proton has spin 1/2,.

o €Hence every energy level associated with a particular set of quantum numbers n, l, and j will
be split into two levels of slightly different energy, depending on the relative orientation of the
proton magnetic dipole with the electron state.

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 Hyperfine structure: Nuclear moments

o The energy splitting of the hyperfine interaction is

given by
F=1
a
ΔE HFS = [ f ( f + 1) − i(i + 1) − j ( j + 1)]
2
F=0
where a is the hyperfine structure constant.

€
o E.g., consider the ground state of H-atom. Nucleus
consists of a single proton, so I = 1/2. The hydrogen
ground state is the 1s 2S1/2 term, which has J = 1/2.
Spin of the electron can be parallel (F = 1) or
QuickTime™ and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

antiparallel (F = 0). Transitions between

€ these levels
occur at 21 cm (1420 MHz).

o For ground state of the hydrogen atom (n=1), the 21 cm radio map of the Milky Way
energy separation between the states of F = 1 and F =
0 is 5.9 x 10-6 eV.

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 Selection rules

o Selection rules determine the allowed transitions between terms.

n = any integer l = ±1 j = 0, ±1 f = 0, ±1

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 Summary of Atomic Energy Scales
o Gross structure:
o Covers largest interactions within the atom:
o Kinetic energy of electrons in their orbits.
o Attractive electrostatic potential between positive nucleus and negative electrons
o Repulsive electrostatic interaction between electrons in a multi-electron atom.
o Size of these interactions gives energies in the 1-10 eV range and upwards.
o Determine whether a photon is IR, visible, UV or X-ray.

o Fine structure:
o Spectral lines often come as multiplets. E.g., H line.
=> smaller interactions within atom, called spin-orbit interaction.
o Electrons in orbit about nucleus give rise to magnetic moment
of magnitude B, which electron spin interacts with. Produces small shift in energy.

o Hyperfine structure:
o Fine-structure lines are split into more multiplets.
o Caused by interactions between electron spin and nucleus spin.
o Nucleus produces a magnetic moment of magnitude
~B/2000 due to nuclear spin.
o E.g., 21-cm line in radio astronomy.

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