PHY420: Problem Set
1. Consider the Beryllium atom with Z = 4.
a. Write the electronic configuration.
b. Setup the ground state wavefunction using the Slater determinant.
c. What is the significance of the Slater determinant?
d. What is the term symbol for the ground state?
2. Consider an atomic state in L = 2 and S = 1.
a. Find possible J quantum numbers.
b. Assuming HLS = C L · S, obtain the expression for the energy EJ with L-S correction
in terms of uncorrected energy E0 , fine-structure constant C, and the quantum numbers
J, L, and S.
c. Draw the energy level diagram consistent with Hund’s rules and label each level with
appropriate term symbol. Indicate the energy gaps in units of C.
3. Consider Silicon atom with atomic number 14.
a. Write its electronic configuration.
b. List out all the terms without considering the L-S interaction. Represent them in an
energy level diagram.
c. Now introduce L-S interaction. Expand the energy level diagram showing splittings due
to L-S interaction. Label all levels by appropriate terms.
4. Consider an atomic state np n0 d configuration.
a. Find all possible terms without fine-structure interaction. Represent the terms using an
energy-level diagram.
b. Now split the levels according to fine-structure interaction. Label each level by the
appropriate term symbol.
5. Consider the Morse potential for diatomic molecule,
2
VM (R) = De 1 − e−β(R−R0 ) ,
where R is the internuclear distance, R0 is the equilibrium bond length, De is the dissociation
energy and β is a Morse parameter.
a. Find the lowest order expansion of VM around R = R0 , and show that it corresponds to
a Harmonic potential. Under this approximation, express energy level separation ~ω in
terms of De , β, and the reduced mass of the molecule µ.
b. In a perfect harmonic oscillator, the energy separation remains constant, while in the
Morse potential the energy separation ∆E(v) decreases linearly with the vibrational
quantum number v. The anharmonicity A of the molecule is given by
∆E(ν) = E(ν + 1) − E(ν) = ~ω − 2A~(ν + 1).
At some quantum number νmax the energy level separation ∆E(ν) becomes minimum
and beyond that the molecule dissociates. Express νmax in terms of ω and A. Express
E(νmax ), the energy corresponding to νmax , in terms of νmax , ω, and A. Setting E(νmax ) =
De , express A in terms of β and µ.
6. The rotational spectrum of HF molecule shows characteristic absorption lines separated by
wavenumber 40.5 cm−1 .
a. Estimate the moment of inertia of the molecule.
b. Using the mass numbers 1 and 19 for H and F respectively, estimate the equilibrium
bond length of the molecule.
c. One could estimate the relative populations of various rotational levels by analyzing the
intensities of the absorption lines. Suppose the population ratio of K = 1 to K = 0
rotational level is 1/e. Estimate the temperature of the gas.
7. The dissociation energy of H2 molecule is 4.74 eV, while its fundamental vibrational wave
number is 4395 cm−1 . Assuming the depth of the well and the force constant for the deuterium
molecule D2 to be equal to those of H2 molecule, find the dissociation energy of D2 molecule.
8. The dissociation energy of H2 molecule is 4.74 eV, while its fundamental vibrational wave
number is 4395 cm−1 . Assuming the depth of the well and the force constant for the deuterium
molecule D2 to be equal to those of H2 molecule, find the dissociation energy of D2 molecule.
9. The Bloch equations are phenomenological equations describing dynamics of the ensemble
magnetization M of single nuclear spins. They can be written in the following form:
Mx − T12 γBz −γBy Mx 0
d
My = −γBz − T12 γBx My + 0 ,
dt M0
Mz γBy −γBx − T11 Mz T1
where {Bx , By , Bz } are the x, y components of RF and the offset respectively. Also, T1 and
T2 are the spin-lattice and spin-spin relaxation constants. Solve the above equations for the
case Bx = By = 0 and obtain Mx (t), My (t), and Mz (t).
10. Consider the NH2 · radical. Here 14 N is spin 1 nucleus. Let aN and aH be the hyperfine
coupling constants of the electron with the nitrogen nucleus and with each of the protons.
Given aN aH . Predict the ESR spectrum of NH2 · radical. Label each peak with its relative
intensity and frequency.
