Chapter 2 - Structure of Hydrogen Atom

Chapter 2 - Structure of hydrogen atom

Section 2.1 - Hydrogen Atom quantum description

Werner Heisenberg
(1901-1976)
The atom of modern physics can be symbolized only through a partial differential equation in an
abstract space of many dimensions. All its qualities are inferential; no material properties can be
directly attributed to it. An understanding of the atomic world in that primary sensuous fashion…is
impossible.
- Werner Heisenberg
Chapter 2 - Structure of hydrogen atom
Hydrogen Atom as a mechanical system problem

Atom is a 3D object, and the electron motion is three-dimensional. We’ll start with the simplest case
- a hydrogen atom. An electron and a proton (nucleus) are bound by the central-symmetric Coulomb
interaction. Because mp>>me, we neglect the proton motion (the reduced mass is very close to me, the
center of mass of this system is ~2000 times closer to the proton than to the electron). Thus, we can
treat this problem as the motion of an electron in the 3D central-symmetric Coulomb potential.

Three dimensions – we expect that the motion will be

characterized with three quantum numbers (in fact,
there will be the fourth one, the electron spin, which
corresponds to the “internal degree of freedom” for an
electron; the spin will be added later “by hand”, it is not
described by the non-relativistic quantum mechanics).
e2
U U r  
4 0r E < 0 – bound motion, discrete spectrum,
E > 0 – unbound motion, continuous spectrum

The task : solve the t-independent S.Eq. for E<0, find the energy eigenvalues (the spectrum) and
eigenfunctions (stationary states).
Chapter 2 - Structure of hydrogen atom
Orbital Motion in Classical Mechanics
 
r v We consider the case of a central force: the force is directed along the line that connects
the electron and proton or, in our Figure, the electron and the coordinate origin.
Coulomb interaction is responsible for acceleration:

F 
e2  mv2 
r  2 r
 mv2  Kinetic mv 2
p 2
 pr
2
 pt 
2

F   K   
4 0r 3
r  r 
energy: 2 2m 2m
pr and pt – the radial and tangential components of the momentum

          
The angular momentum Lrp L  r  p  r   pr  pt   r  pt

K
 p 2
r  pt2 

pr2

L2 For a circular K
L2
2m 2m 2mr 2 motion: 2mr 2

 dL
In general, a non-zero torque leads to the time dependence of L: 
  dt
In the field of a central force, the torque is  dL  dp  
   r   r F  0
zero, and the angular momentum about the dt dt 
center is conserved:

r is antiparallel to F 
This makes L especially useful for analyzing the central force motion.
Chapter 2 - Structure of hydrogen atom
Quantum Mechanical Approach

  x, y, z, t   2     x, y, z, t     x, y, z, t     x, y, z, t  
2 2 2

i       U  x, y , z    x, y , z , t 
t 2m  x 2 y 2 z 2 
e2 e2
U  x, y, z     - potential energy of Coulomb interaction
4 0 x  y  z
2 2 2 4 0r between electron and proton

Laplacian 2  d d d  
pˆ       
i  dx dy dz  i
  x, t  ˆ  
2 2 2 2
ˆ  d d d
i  H   x, t  H   2  2  2   U ( x, y , z )
t 2m  dx dy dz 

K operator U operator

The potential is time-independent, thus we can separate time and space variables:

dT  t   iEt 
i  ET  t  Hˆ  x, y, z   E  x, y, z    x, t    E  x  exp  
dt   
Chapter 2 - Structure of hydrogen atom
Application of the Schrödinger Equation to the Hydrogen Atom

The potential energy of the electron-proton system is electrostatic:

Use the three-dimensional time-independent Schrödinger Equation.

For Hydrogen-like atoms (He+ or Li++), replace e2 with Ze2 (Z is the atomic
number).
In all cases, for better accuracy, replace m with the reduced mass, .
Chapter 2 - Structure of hydrogen atom
Isotropy of the system - Spherical coordinates

The Coulomb potential has central symmetry (U(r)

depends on neither nor ). It’s to our advantage to
use spherical polar coordinates (this will allow us to
separate variables).

r  x2  y 2  z 2 - distance from
origin to point P
z
  cos1
x2  y 2  z 2 - zenith angle

y
  tan 1
x - azimuth angle

- a (small) volume element used for

integration (no relation to the torque )
Chapter 2 - Structure of hydrogen atom
Application of the Schrödinger Equation to the Hydrogen Atom

The Schrödinger
Equation in
Spherical
Coordinates

Transformed into
spherical coordinates,
the Schrödinger
equation becomes:
Chapter 2 - Structure of hydrogen atom
Properties of the Hamiltonian - Separable solution

The wave function  is a function of r, , . This is a potentially complicated

function.

Assume instead that  is separable, that is, a product of three functions, each of one
variable only :
Chapter 2 - Structure of hydrogen atom
Solution to the Schrödinger equation for hydrogen

Start with Schrodinger’s Equation:

Substitute:

Multiply both sides by r2 sin2 / R f g:

Chapter 2 - Structure of hydrogen atom
Solution to the Schrödinger equation for hydrogen

r and  appear only on the left side and  appears only on the right side.
The left side of the equation cannot change as  changes.
The right side cannot change with either r or .

Each side needs to be equal to a constant for the equation to be true.

Set the constant to be −mℓ2

azimutal equation

It is convenient to choose the solution to be

Chapter 2 - Structure of hydrogen atom
Azimutal part of the eigenfunctions
d 2 ˆL   
 ml0
2 - the angular momentum along this axis is the
 2 z
i  “generator” of rotation around this axis

Lˆ2z   2ml2   Aei ml  The wavefunction must be single-valued, thus

i ml  i ml   2 
Ae  Ae ml must be integer

ml – the magnetic quantum number

What is the range of ml variations?

1 d     ml2 
 l  l  1  2    0
- this Eq. has a
sin   l  ml
sin  d     sin   solution provided

Thus, ml  0, 1, 2,......, l

Discrete eigenvalues of the
angular momentum along z axis: 
Lˆz   Aeiml  ml 
i
Lz  ml
Chapter 2 - Structure of hydrogen atom
Solution to the Schrödinger equation for hydrogen

Now set the left side equal to −mℓ2:

−mℓ2

Rearrange it and divide by sin2():

Now, the left side depends only on r, and the right side depends only on .
Chapter 2 - Structure of hydrogen atom
Solution to the Schrödinger equation for hydrogen

Set each side equal to the constant ℓ(ℓ + 1).

Radial equation

Angular equation

We’ve separated the Schrödinger equation into three ordinary second-order differential
equations, each containing only one variable.
Chapter 2 - Structure of hydrogen atom
Solution to the Radial equation for hydrogen

The radial equation is called the associated Laguerre equation and the solutions R are
called associated Laguerre functions. There are infinitely many of them, for values of n
= 1, 2, 3, …

Assume that the ground state has n = 1 and ℓ = 0. Let’s find this solution.
The radial equation becomes :

The derivative of yields two terms :

Chapter 2 - Structure of hydrogen atom
Solution to the Radial equation for hydrogen

Try a solution
A is a normalization constant.
a0 is a constant with the dimension of length.
Take derivatives of R and insert them into the radial equation.

To satisfy this equation for any r, both expressions in parentheses must be zero.

Set the second expression

equal to zero and solve for a0:

Set the first expression equal

to zero and solve for E:

Both are equal to the Bohr results !

Chapter 2 - Structure of hydrogen atom
Comparison with Bohr’s Model

Niels Bohr (1913) (a decade before de Broglie’s work !) proposed the first successful
semi-classical model of an atom: circular electron motion as a standing wave.

Below we consider this model using de Broglie terminology: an electron can circle a nucleus
only if its orbit contains an integer number of de Broglie wavelengths.

h h 4 0r n2h2 0
n  2 rn   rn   n 2
r1 n  1, 2, 3,...
p e m  me 2

e2 e2 e2
En  K  U    Combining these two equation, we get the

8 0rn 4 0rn 8 0rn

correct formula for the energy eigenvalues

me4  1  E1
En   2 2 2  2 
 2 n  1, 2, 3,... (one of the most successful wild guesses ever made)
32  0   n  n

This model has a huge historical importance, but because of its semi-classic nature (orbits, etc.), it is a poor and
misleading picture of what is really going on in H atom. The difference between the probability to find an electron at
some distance r from the nucleus according to Bohr model and that in the quantum model is dramatic at lower n: e.g., at
n=0 (the ground state), according to quantum mechanics the angular momentum is 0, and the probability peaks at the
nucleus position!
Chapter 2 - Structure of hydrogen atom
Solution to the Radial equation for hydrogen

Principal quantum number n

There are many solutions to the radial wave equation, one for each positive
integer, n.

The result for the quantized energy is:

A negative energy means that the electron and proton are bound together.
Chapter 2 - Structure of hydrogen atom
Quantum numbers in hydrogen atom

The three quantum numbers:

n : Principal quantum number
ℓ : Orbital angular momentum quantum number
mℓ : Magnetic (azimutal) quantum number

The restrictions for the quantum numbers:

n = 1, 2, 3, 4, . . .
ℓ = 0, 1, 2, 3, . . . , n − 1
mℓ = −ℓ, −ℓ + 1, . . . , 0, 1, . . . , ℓ − 1, ℓ

Equivalently:
n>0
ℓ<n The energy levels are:
|mℓ| ≤ ℓ
Chapter 2 - Structure of hydrogen atom
Optical spectrum of hydrogen

Bohr’s formula:
Chapter 2 - Structure of hydrogen atom
Hydrogen Atom Radial Wave Functions

2.1

First few radial

wave functions Rnℓ

Sub-scripts on R
specify the values of
n and ℓ.
Chapter 2 - Structure of hydrogen atom
Solution to the Angular and azimutal equation for hydrogen

The solutions to the azimutal equation

are : with mℓ integer

Solutions to the angular and azimutal

equations are linked because both have
mℓ as integer parameter (state
equation)

Physicists usually group these

solutions together into functions called
Spherical Harmonics:
Chapter 2 - Structure of hydrogen atom
Solution
Total wave
to the
function
Angular
and
and
probability
azimutal equation
distribution
for function
hydrogen

Wave Function
The radial wave function R and the spherical harmonics Y determine the probability density
for the various quantum states. The total wave function depends on n, ℓ,
and mℓ. The wave function becomes

Probability distribution function

We use the wave functions to calculate the probability distributions of the electrons.
The “position” of the electron is spread over space and is not well defined.
We may use the radial wave function R(r) to calculate radial probability distributions of the
electron.
The probability of finding the electron in a differential volume element d is:
Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

The differential volume element in spherical polar coordinates is

Therefore,

At the moment, we’re only interested in the radial dependence.

The radial probability density is P(r) = r2|R(r)|2 and it depends only on n and ℓ.
Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

Probability
Distribution
Functions

R(r) and P(r) for the lowest-

lying states of the hydrogen
atom.
Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

For all s-states, the angular momentum is zero: n  1, 2, 3,... l  0 ml  0

n=2

n=3

“Boundary” sphere: r1s = 1.4 Å, r2s = 3.3 Å, r3s = 10 Å

Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

2

Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

Note that there are three different configurations

corresponding to m = -1, 0, 1
2p Orbitals
Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

3d Orbitals

4f
Orbitals
Chapter 2 - Structure of hydrogen atom
Solution to the
Probability
Angular and
distribution
azimutal equation
function for hydrogen

oThe probability density for the hydrogen atom for three different electron states.
Chapter 2 - Structure of hydrogen atom
Solution
Orbital
to the
angular
Angular
momentum
and azimutal
and quantum
equationnumber
for hydrogen
l

Energy levels are degenerate with respect to ℓ (the energy is independent of ℓ).
Physicists use letter names for the various ℓ values:
ℓ= 0 1 2 3 4 5...
letter = s p d f g h...
Atomic states are usualy referred to by their values of n and ℓ.
A state with n = 2 and ℓ = 1 is called a 2p state.

Angular Orbital Momentum

It’s associated with the R(r) and f(θ) parts of the wave function.
Classically, the orbital angular momentum with L = mvorbitalr.
L is related to ℓ by
In an ℓ = 0 state,
This disagrees with Bohr’s semi-classical “planetary”
model of electrons orbiting a nucleus L = nħ.

Classical orbits—which do not exist in

quantum mechanics
Chapter 2 - Structure of hydrogen atom
Solution to the Magnetic
Angular and
quantum
azimutal
number
equation
ml for hydrogen

The solution for g() specifies that mℓ is

an integer and is related to the z
component of L:

Example: ℓ = 2:

Only certain orientations of are possible.

This is called space quantization.

And (except when ℓ = 0) we just don’t

know Lx and Ly !
Chapter 2 - Structure of hydrogen atom
Solution to theRough
Angular and azimutal
derivation of ‹L2› =equation
ℓ(ℓ+1)ħ2 for hydrogen

We expect the average of the angular momentum components squared to be the

same due to spherical symmetry:

But

Averaging over all mℓ values (assuming each is equally likely) :

Because : 
n  
m 2  (  1)(2  1) / 3
Chapter 2 - Structure of hydrogen atom
Section 2.2 - Magnetic Effects on Atomic Spectra

In 1896, the Dutch physicist Pieter Zeeman

showed that spectral lines emitted by atoms
in a magnetic field split into multiple energy
levels. It is called the Zeeman effect.
Consider the atom to behave like a small magnet.
Think of an electron as an orbiting circular current loop of I = dq / dt around the
nucleus. If the period is T = 2r / v,

then I = -e/T = -e/(2r / v) = -e v /(2r).

The current loop has a magnetic moment  = IA = [-e v /(2r)] r2 =

[-e/2m] mrv : 
 e
 L
2m
where L = mvr is the magnitude of the orbital angular momentum.
Chapter 2 - Structure of hydrogen atom
The Zeeman Effect

 e 
 L
2m
The potential energy due to the magnetic
field is :

If the magnetic field is in the z-direction, we only care about the z-component of :

e e
z   Lz   (m )    B m
2m 2m

where B = eħ / 2m is called the Bohr magneton.

Chapter 2 - Structure of hydrogen atom
The Zeeman Effect

A magnetic field splits the mℓ levels. The potential energy is quantized and now also
depends on the magnetic quantum number mℓ.

When a magnetic field is applied, the 2p level of atomic hydrogen is split into three
different energy states with energy difference of ΔE = BB Δmℓ.

mℓ Energy

1 E0 + μBB

0 E0

−1 E0 − μBB
Chapter 2 - Structure of hydrogen atom
The Zeeman Effect

The Zeeman
Effect

The transition from 2p to 1s,

split by a magnetic field.
Chapter 2 - Structure of hydrogen atom
The Zeeman Effect

An atomic beam of particles in the ℓ = 1 state pass through a magnetic field along
the z direction.

   B m (dB / dz )
The mℓ = +1 state will be deflected down, the mℓ = −1 state up,
and the mℓ = 0 state will be undeflected.
Chapter 2 - Structure of hydrogen atom
Energy levels and electron transition probabilities

Energy Levels and

Electron Transitions

For hydrogen, the energy level

depends on the principal quantum
number n.

In the ground state, an atom cannot

emit radiation. It can absorb
electromagnetic radiation, or gain
energy through inelastic
bombardment by particles.
Chapter 2 - Structure of hydrogen atom
Dipolar Radiative Transition - Selection Rules

We can use the wave functions to calculate transition probabilities

for the electron to change from one state to another.

The probability is proportional to

the mag square of the  where i and f



dipole moment:
d   f er  i
*
are the initial and
final states of the
transition.
Allowed transitions:
Electrons absorbing or emitting photons can change states when Δℓ = ±1
and Δmℓ = 0, ±1.

Forbidden transitions:
Other transitions are possible
but occur with much smaller
probabilities.
Chapter 2 - Structure of hydrogen atom
Intrinsic Spin

In 1925, grad students, Samuel Goudsmit and George Uhlenbeck, in Holland proposed
that the electron must have an intrinsic angular momentum and therefore a magnetic
moment.
Paul Ehrenfest showed that, if so, the surface of the spinning electron should be moving
faster than the speed of light!
In order to explain experimental data, Goudsmit and Uhlenbeck
proposed that the electron must have an intrinsic
spin quantum number s = ½.
The spinning electron reacts similarly to the orbiting electron in a magnetic field.
The magnetic spin quantum number ms has only two values, ms = ±½.

The electron’s spin will be either “up” or “down”

and can never be spinning with its magnetic moment
μs exactly along the z axis.
Chapter 2 - Structure of hydrogen atom
Intrinsic Spin

The magnetic moment is .

The coefficient of is −2μB and is a
 e 
consequence of relativistic quantum mechanics. analogy L   L
2m
Writing in terms of the gyromagnetic ratio, g: gℓ = 1 and gs = 2:

and

The z component of .
In an ℓ = 0 state: no splitting due to .

Apply ms and the potential energy becomes:

Chapter 2 - Structure of hydrogen atom
Section 2.3 - 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.
Chapter 2 - Structure of hydrogen atom
Spin-orbit coupling in H-atom

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

Jˆ is a max
Z ˆ ˆ
E so   SL
 2m 2
cr 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  2Sˆ  Lˆ
1
Sˆ  Lˆ  ( Jˆ  Jˆ  Lˆ  Lˆ  Sˆ  Sˆ ) +Ze
2
-e
ˆ ˆ 2
 S  L  [ j( j  1)  l(l  1)  s(s  1)]
 2 Sˆ
Z 3 1
 E so   [ j( j  1)  l(l  1)  s(s  1)]
 4m 2c r 3
Chapter 2 - Structure of hydrogen atom
Spin-orbit effects in H fine structure

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

a
E so 
2
j  j  1  l(l  1)  ss  1
where a  Ze 20  2 /8m 2 r 3 is the spin-orbit coupling constant. Therefore, for the 2p
electron:
a 3 3  1 1  1
E so     11(1 1)    1  a
2 2 2  2 2  2
a 1 1  1 1 
E 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
Chapter 2 - Structure of hydrogen atom
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 :
n 22
r  4 0
mZe 2
Z4
 a ~ 6
 n
o Spin-orbit coupling increases sharply with Z. Difficult to observe 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 2 4 2 [ j( j  1)  l(l  1)  3/4]

E so  mc
2n 3 l(l  1)(2l  1)
Chapter 2 - Structure of hydrogen atom
Spin-orbit coupling - 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+1L

J

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.

Chapter 2 - Structure of hydrogen atom
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:

2P
+1/2a
E 3/2 Angular momenta aligned
2p1 (2P)

-a
2P
1/2 Angular momenta opposite
Chapter 2 - Structure of hydrogen atom
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.
Chapter 2 - Structure of hydrogen atom
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 2 4  1 3 
E 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 of Dirac equation.
Chapter 2 - Structure of hydrogen atom
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 4 4 2  1 3 
E FS  E so  E 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 2 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.
Chapter 2 - Structure of hydrogen atom
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!
Chapter 2 - Structure of hydrogen atom
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 Rutherford showed in 1947 that 22S1/2 (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.
Chapter 2 - Structure of hydrogen atom
Hyperfine structure - Lamb shift - Experiment

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 22S1/2 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.
Chapter 2 - Structure of hydrogen atom
Hyperfine structure - Lamb shift - Quantum electrodynamics

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
Rutherford 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

Chapter 2 - Structure of hydrogen atom
Hyperfine structure - Nuclear momentum

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.

o ˆ nucleus  Bˆ electron  Iˆ  Jˆ
Interaction energy is therefore E hyperfine  

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.
Chapter 2 - Structure of hydrogen atom
Hyperfine structure - Nuclear momentum

o Like electron, the proton has a spin angular momentum and an associated intrinsic dipole
moment e ˆ

ˆ p  gp 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 Resulting energy correction can be shown to be: E p  2 3
Iˆ  Jˆ
mMc r
o Total angular momentum including nuclear spin, orbital angular momentum and electron spin
is ˆ ˆ ˆ
FIJ
where F f ( f  1)
F  mf 
 z
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.
Chapter 2 - Structure of hydrogen atom
Hyperfine structure - Nuclear momentum

o The energy splitting of the hyperfine interaction is

given by
F=1
a
E 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.
Chapter 2 - Structure of hydrogen atom
Radiative transitions - Selection rules

o Selection rules determine the allowed transitions between terms.

n = any integer l = ±1 j = 0, ±1 f = 0, ±1
Chapter 2 - Structure of hydrogen atom
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.