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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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A hydrogen-like atom
A hydrogen-like atom is an atom consisting of a nucleus and just one electron; the nucleus can be bigger than just
a single proton, though. H atoms, He+ ions, Li2+ ions etc. are hydrogen-like atoms in this context. Our aim is to
develop the exact solution for the hydrogen-like atom as an approximation for multi-electron atoms.
The potential, V between two charges is best described by a Coulomb term,

where Ze is the charge of the nucleus (Z=1 being the hydrogen case, Z=2 helium,
etc.), the other e is the charge of the single electron, ϵ0 is the permittivity of vacuum
(no relative permittivity is needed as the space inside the atom is "empty").
With the system consisting of two masses, we can define the reduced mass, i.e. the equivalent mass a point located
at the centre of gravity of the system would have

where M is the mass of the nucleus and m the mass of the electron.
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Thus, the hydrogen atom's Hamiltonian is

The del operator in spherical coordinates

The Schrödinger equation of the hydrogen atom in polar coordinates is:

Both LHS and RHS contain a term linear in ψ, so combine:

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Using the Separation of Variables idea, we assume a product solution of a radial and an angular function:

Since Y does not depend on r , we can move it in front of the radial derivative:

and, similarly, R does not depend on the angular variables. Thus replace ψ and the differentials:

Multiply by r2 and divide by RY to separate the radial and angular terms:

The first and fourth terms depend on r only, the middle terms depend on the angles only. They can only balance
each other for all points in space if the radial and angular terms are the same constant but with opposite sign.
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Therefore, we can separate into a radial equation:

and an angular equation:

where A is the separation constant.

Separating the angular part into polar and azimuth parts

The angular part still contains terms depending on both θ and ϕ. Another separation of variables is needed.
We'll replace Y by a product of single-variable functions:

Replacing Y and the differentials, we have

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Isolate variables in separate terms:

With B as separation constant, we have a polar part:

and an azimuth part:

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Solving the azimuth equation

The azimuth equation:

is a 2nd order ODE with constant coefficients solved by:

where 𝐵 = 𝑚2.
The angle 𝜙 is the azimuth, a mathematically convenient way is by setting 𝑐2 = 0.

Note that m must be an integer number - otherwise the value of the azimuth wave function would be different for 𝜙 =
0𝑜 and 𝜙 = 360𝑜 . In quantum terminology, 𝑚 is called a quantum number as it restricts the possible values of the
wave function (and hence of observables) to integer multiples (quanta) of a base unit.
Thus, the azimuth part of the wave function is
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Solving the polar equation

With B=m2, the polar equation is:

Rearrange:

Substituting 𝑃(cos𝜃): = Θ(𝜃) and 𝑥: = cos𝜃 and hence the differential,

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Tidy up:

Because of sin2𝜃 + cos2𝜃 = 1, we can further substitute sin2𝜃 = 1 − cos2𝜃 = 1 − 𝑥2 and get

Apply the product rule to the first term:

This type of differential equation (called associated Legendre-type DE), for which a solution is known in the math's
literature. The solutions are known as associated Legendre polynomials, and they contain a power series with
recursive coefficients.
Legendre's polynomials:

with the coefficients

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This means that there are two power series (for the even and odd terms, respectively) and that the coefficients of
the higher terms can be calculated recursively if the first coefficient of each series, 𝑎0 and 𝑎1
For the recursion formula above, the series converges if 𝐴 = 𝑙(𝑙 + 1) where 𝑙 is an integer number. The root
coefficients of the two series, 𝑎0 and 𝑎1, are chosen depending on the particular value of 𝑙 to ensure only the
convergent series survives. The first few Legendre functions are:

The value of 𝑙 limits the choices of 𝑚; 𝑚 must have a value between −𝑙 and 𝑙. As far as the polar part is
concerned, the ±𝑚 solutions are equivalent, but the sign of 𝑚 makes a difference to the azimuth part as seen
above.
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Solving the radial equation

In the radial equation,

r →

apply the product rule to the first term:

and divide by 𝑟2:

Case 1. The asymptotic solution 𝑟 → ∞

We can't solve this straight away, but for very large 𝑟, the highlighted terms are forced to zero because they go
reciprocal with 𝑟.
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That leaves us with an asymptotic equation

which is another ODE with constant coefficients. Solution:

It makes sense to use as the zero point of potential energy the energy of a free electron, i.e. in this asymptotic
case, 𝐸 → 0 for an electron far away from the nucleus, as it is practically free. Since the presence of the positive
charge in the nucleus stabilises the atom, we must look for solutions where 𝐸 becomes negative as the electron
comes closer to the nucleus. These two conditions are met if we choose 𝑐4 = 0 and use the fact that 𝐸 < 0 to get
rid of the imaginary unit.

The asymptotic solution is then

Case 2. The detail nearer the nucleus is expanded in a power series: 𝑟 → 0

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This results in a series of powers of 𝑟 whose coefficients must all be zero to match the RHS of the differential
equation. From that, a recursion formula is derived for the 𝑏𝑞 , and the requirement for the series to converge
produces another quantum number, 𝑛.
This results in the radial solution

where the coefficient 𝑏0 contains the 𝑙-dependence.

At the same time, the solution of the radial part also fixes the possible energy levels by linking them to the quantum
number 𝑛. The energy levels of the hydrogen-like atom are given by

Putting the partial solutions together

The full solution of the Schrödinger equation of the hydrogen-like atom is, according to the separation approach
taken:
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QUANTUM NUMBERS
Three dimensions, three quantum numbers
The first of these equations, is readily solved. The result is

one of the conditions that a wave function—and hence φ, which is a component of the complete wave function —
must obey is that it have a single value at a given point in space.

it is clear that 𝜑 and 𝜑 + 2𝜋 both identify the same meridian plane. Hence it
must be true that

which can happen only when 𝑚𝑙 is 0 or a positive or negative integer

The constant ml is known as the magnetic quantum number of the hydrogen atom.
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The differential equation for

has a solution provided that the constant 𝑙 is an integer equal to or greater than ml the absolute value of 𝑚𝑙. This
requirement can be expressed as a conditionm on 𝑚𝑙 in the form
l

The constant 𝑙 is known as the orbital quantum number.

The solution of the final equation, for the radial part 𝑅(𝑟) of the hydrogen atom wave function also requires that a
certain condition be fulfilled. This condition is that 𝐸 be positive or have one of the negative values 𝐸𝑛 (signifying
that the electron is bound to the atom) specified by
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Another condition that must be obeyed in order to solve the differential equation is that 𝑛, known as the principal
quantum number, must be equal to or greater than 𝑙 + 1.
This requirement may be expressed as a condition on 𝑙 in the form

Hence we may tabulate the three quantum numbers 𝑛, 𝑙, and 𝑚 together with their permissible values as follows:

To exhibit the dependence of R, , and upon the quantum numbers n, l, m, we may write for the electron wave
functions of the hydrogen atom
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