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ATOMIC AND MOLECULAR

SPECTROSCOPY
PHY424
Prof. Odo Ayodele
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Course Content
ATOMIC AND MOLECULAR SPECTROSCOPY: (3 Units) Pre-requisite -PHY 201.
1. The hydrogen atom, relativistic effects and spin.
2. Identical particles and symmetry.
3. Many electron atoms.
4. Coupling schemes and vector model.
5. Zeeman effects.
6. Stack effects.
7. Hyperfine structure.
8. The diatomic molecule; the Frank-Condon principle.
9. X-ray diffraction.
10. Microwave methods.
11. Resonance phenomena: ESR, NMR.
12. Resonance phenomena: Optical pumping and Mossbauer scattering.
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PRINCIPAL QUANTUM NUMBER

In the hydrogen atom the electron energy is a constant, its values can are specified by the formula .
𝐸𝑛 = 𝐸1 /𝑛2
The quantization of electron energy in the hydrogen atom is therefore described by the principal quantum number
𝑛.
ORBITAL QUANTUM NUMBER
Quantization of angular-momentum magnitude
Let us look at the differential equation for the radial part 𝑅(𝑟) of the wave function :

Eq. (Q1)

This equation is solely concerned with the radial aspect of the electron’s motion, that is, its motion toward or
away from the nucleus.
However, the total energy 𝐸 includes the electron’s kinetic energy of orbital motion, which should have nothing to do
with its radial motion.
The kinetic energy 𝐾𝐸 of the electron has two parts, 𝐾𝐸𝑟𝑎𝑑𝑖𝑎𝑙 due to its motion toward or away from the nucleus, and
𝐾𝐸𝑜𝑟𝑏𝑖𝑡𝑎𝑙 due to its motion around the nucleus. The potential energy 𝑈 of the electron is the electric energy
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Hence the total energy of the electron is

Eq. (Q2)

Inserting this expression for 𝐸 in Eq. (Q1) we obtain, after a slight rearrangement,

Eq. (Q3)

If the last two terms in the square brackets of this equation cancel each other out, we shall have what we want: a
differential equation for 𝑅(𝑟) that involves functions of the radius vector 𝑟 exclusively

We therefore require that Eq. (Q4)

Since the orbital kinetic energy of the electron and the magnitude of its angular momentum are respectively

Eq. (Q5)
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Hence, from Eq. (Q4),

Electron angular momentum Eq. (Q6)

With the orbital quantum number 𝑙 restricted to the values

The electron can have only the angular momenta 𝐿 specified by Eq. (Q6), Like total energy 𝐸, angular momentum is
both conserved and quantized.

Designation of Angular-Momentum States

It is customary to specify electron angular-momentum states by a letter, according to the following scheme:

Thus an 𝑠 state is one with no angular momentum, a 𝑝 state has the angular moment

The combination of the total quantum number with the letter that represents orbital angular momentum provides a
convenient and widely used notation for atomic electron states.
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Atomic Electron States

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MAGNETIC QUANTUM NUMBER

Quantization of angular-momentum direction

The orbital quantum number 𝑙 determines the magnitude L of the electron’s angular momentum 𝐿.
However, angular momentum, like linear momentum, is a vector quantity
𝐿, we recall, is perpendicular to the plane in which the rotational motion takes place, and its sense is given by the
right-hand rule:

An electron revolving about a nucleus is a minute current loop and has a

magnetic field like that of a magnetic dipole. Hence an atomic electron
that possesses angular momentum interacts with an external magnetic
field 𝐵.
The magnetic quantum number 𝑚𝑙 specifies the direction of 𝐿 by
determining the component of 𝐿 in the field direction.
This phenomenon is often referred to as space quantization.
If we let the magnetic-field direction be parallel to the 𝑧 axis, the component of 𝐿
in this direction is
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The possible values of 𝑚𝑙 for a given value of 𝑙 range from +𝑙 through 0 to −𝑙 so that the number of possible
orientations of the angular-momentum vector 𝐿 in a magnetic field is 2𝑙 + 1.
In particular, for a fixed 𝑙 the particle energy 𝐸 is independent of 𝑚𝑙 and so is at
least 2𝑙 + 1 -fold degenerate. Such degeneracy—a property of all central
forces—stems from the spherical symmetry of the potential
Note that 𝐿 can never be aligned with the 𝑧-axis, since 𝐿𝑧 must be smaller than
the total angular momentum 𝐿. From a three-dimensional perspective, 𝐿 must
lie on the surface of a cone that makes an angle 𝜃 with the 𝑧-axis, as shown in
Figure b.
According to quantum mechanics, the possible
orientations for 𝐿 are those consistent with Equation.
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EXAMPLE 1 Orbital Quantum Number for a Stone

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EXAMPLE 2 The Bohr Atom Revisited

Discuss angular momentum quantization in the Bohr model. What orbital quantum number describes the electron in
the first Bohr orbit of hydrogen?

Solution
Angular momentum in the Bohr atom is quantized according to the Bohr postulate

with 𝑛 = 1 for the first Bohr orbit. Comparing this with the quantum mechanical result,
we see that the two rules are incompatible! The magnitude L can never be an integral multiple of ℎ —the
smallest nonzero value consistent with quantum mechanical result is
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EXAMPLE 3 Space Quantization for an Atomic Electron

Exercise Compare the minimum angles between 𝐿 and the 𝑧-axis for the electron of Example 3 and for the 1.00-
kg stone of Example 1.
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RADIATIVE TRANSITIONS
For hydrogen-like atoms, then, the quantum numbers are 𝑛, 𝑙 and 𝑚𝑙 associated with the sharp observables 𝐸, 𝐿
and 𝐿𝑧, respectively. Notice that the energy 𝐸 depends on 𝑛, but not at all on 𝑙 or 𝑚𝑙

What happens when an electron goes from one state to another?

In formulating his theory of the hydrogen atom, Bohr was obliged to postulate that the frequency 𝑣 of the radiation
emitted by an atom dropping from an energy level 𝐸𝑚 to a lower level 𝐸𝑛 is

The figure portrays a few of the many electronic transitions

possible within the atom.
Each such transition represents a change of energy for the atom
and must be compensated for by emission (or absorption) of energy
in some other form.
For optical transitions, photons carry off the surplus energy, but not
all energy-conserving optical transitions may occur.
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To conserve total angular momentum (atom + photon) in optical transitions, the angular momentum of the electron
in the initial and final states must differ by exactly one unit, that is

This Equation expresses a selection rule that must be

obeyed in optical transitions.
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EXAMPLE 4 The 𝑛 = 2 Level of Hydrogen

Exercise How many possible states are there for the 𝑛 = 3 level of hydrogen? For the 𝑛 = 4 level?
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The Ground State of Hydrogen-like Atoms

The ground state of a one-electron atom or ion with atomic number 𝑍, for which 𝑛 = 1, 𝑙 = 0, and 𝑚𝑙 = 0, has
energy

The wavefunction for this state is

Notice that 100 does not depend on angle

All the 𝑙 = 0 waves share this feature; that is, all s-state
waves are spherically symmetric.
The electron described by the wavefunction of 100 is
found with a probability per unit volume given by
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Thus, it is convenient to define another probability function, called the radial probability distribution, with its
associated density 𝑃(𝑟), such that 𝑃(𝑟)𝑑𝑟 is the probability of finding the electron anywhere in the spherical shell
of radius r and thickness 𝑑𝑟
The shell volume is its surface area , multiplied by the shell thickness 𝑑𝑟
Since the probability density is the same everywhere in the shell, we have

for the hydrogen-like 1s state,

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A plot of the function P1s(r) is presented in Figure a; Figure b shows the 1s electron “cloud” or probability per unit
volume

P(r) may be loosely interpreted as the probability of finding the electron at distance r from the nucleus, irrespective
of its angular position. Thus, the peak of the curve in Figure a represents the most probable distance of the 1s
electron from the nucleus.
Furthermore, the normalization condition becomes
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where the integral is taken over all possible values of r. The average distance of the electron from the nucleus is
found by weighting each possible distance with the probability that the electron will be found at that distance:

In fact, the average value of any function of distance 𝑓(𝑟) is obtained by weighting the function value at every
distance with the probability at that distance
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EXAMPLE 5 Probabilities for the Electron in Hydrogen

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EXAMPLE 6
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EXAMPLE 7

we have for the ratio of the probabilities that an electron in a hydrogen atom be at the distances 𝑟1 and 𝑟2 from
the nucleus
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Excited States of Hydrogen-like Atoms

There are four first excited states for hydrogen-like atoms:
All have the same principal quantum number 𝑛 = 2, hence the same total energy

Accordingly, the first excited level, 𝐸2, is fourfold degenerate.

The 2s state, , is again spherically symmetric.
Plots of the radial probability density for this and several
other hydrogen-like states are shown in Figure
Note that the plot for the 2s state has two peaks. In this
case, the most probable distance ( ~5𝑎0/𝑍 ) is marked by
the highest peak.
An electron in the 2s state would be much farther from the
nucleus (on the average) than an electron in the 1s state.
Likewise, the most probable distances are even greater
for an electron in any of the 𝑛 = 3 states (3s, 3p, or 3d).
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The remaining three first excited states, and make up the 2p subshell.
These states are not spherically symmetric.
All of them have the same radial wavefunction
𝑅21(𝑟), but they are multiplied by different
spherical harmonics and thus depend
differently on the angles θ and φ
For example, the wavefunction
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Tutorial
1. Why is it natural that three quantum numbers are needed to describe an atomic electron (apart from electron spin)?
2. Compare the angular momentum of a ground-state electron in the Bohr model of the hydrogen atom with its value in
the quantum theory.
3. (a) What is Schrödinger’s equation for a particle of mass m that is constrained to move in a circle of radius R, so that
depends only on  (b) Solve this equation for  and evaluate the normalization constant. (Hint: Review the solution of
Schrödinger’s equation for the hydrogen atom.) (c) Find the possible energies of the particle. (d) Find the possible angular
momenta of the particle.
4. What are the angles between L and the z axis for 𝑙 = 1? For 𝑙 = 2?
5. What are the possible values of the magnetic quantum number 𝑚𝑙 of an atomic electron whose orbital quantum number
is 𝑙 = 4?
6. List the sets of quantum numbers possible for an 𝑛 = 4 hydrogen atom.
7. Verify that the most probable value of 𝑟 for a 1s electron in a hydrogen atom is the Bohr radius 𝑎0.
8. Find the most probable value of 𝑟 for a 3𝑑 electron in a hydrogen atom
9. How much more likely is the electron in a ground-state hydrogen atom to be at the distance a0 from the nucleus than at
the distance 2a0?
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10. The probability of finding an atomic electron whose radial wave function is R(r) outside a sphere of radius r0 centered
on the nucleus is

(a) Calculate the probability of finding a 1s electron in a hydrogen atom at a distance greater than a0 from the nucleus.
(b) When a 1s electron in a hydrogen atom is 2a0 from the nucleus, all its energy is potential energy. According to classical
physics, the electron therefore cannot ever exceed the distance 2a0 from the nucleus. Find the probability r > 2a0 for a 1s
electron in a hydrogen atom.

11. A hydrogen atom is in the 4p state. To what state or states can it go by radiating a photon in an allowed transition?
12. A particle of mass m moves in a three-dimensional box with edge lengths L1, L2, and L3. Find the energies of the six
lowest states if L1 = L, L2 = 2L, and L3 = 2L.Which of these energies are degenerate?
13. An electron moves in a cube whose sides have a length of 0.2 𝑛𝑚. Find values for the energy of (a) the ground state
and (b) the first excited state of the electron.
14. A particle of mass m moves in a three-dimensional box with sides 𝐿. If the particle is in the third excited level,
corresponding to 𝑛2 = 11, find (a) the energy of the particle, (b) the combinations of 𝑛1, 𝑛2, and 𝑛3 that would give this
energy, and (c) the wavefunctions for these different states.
15. A particle of mass m moves in a two-dimensional box of sides 𝐿. (a) Write expressions for the wavefunctions
and energies as a function of the quantum numbers n1 and n2 (assuming the box is in the 𝑥𝑦 plane). (b) Find
the energies of the ground state and first excited state. Is either of these states degenerate? Explain.
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+
16. (a) Determine the quantum numbers 𝑙 and 𝑚𝑙 for the 𝐻𝑒 ion in the state corresponding to 𝑛 = 3. (b)
What
is the energy of this state?
+
17. (a) Determine the quantum numbers 𝑙 and 𝑚𝑙 for the 𝐿𝑖2 ion in the states for which 𝑛 = 1 and 𝑛 = 2.
(b) What are the energies of these states?