UCL PHYSICS AND ASTRONOMY PHAS0023 ICA

ATOMIC AND MOLECULAR PHYSICS

PHAS0023
In Course Assessment – 2022
[The marks for each question are indicated in brackets]

1. Consider the 1s2s excited electronic configuration of the 4 He atom. The

mass of the 4 He atom is M4 He = 6.642 × 10−27 kg.

(a) Determine the two allowed terms associated with this electronic
configuration. [4]
(b) The two terms in part (a) lie 159 855.97 cm−1 and 166 277.44 cm−1
above the ground state.

i. Assign the terms you have identified to these wavenumbers. [2]

ii. What is the origin of the energy difference between these terms? [1]
iii. If the ground state ionisation energy of the helium atom is
198 310.67 cm−1 , calculate the quantum defects associated
with each of the two terms in part (a)? [5]
−1
(Note the Rydberg constant for helium is RHe = 109 722.28 cm )

2. Consider a multielectron atomic state with the term 5 D.

(a) What are the possible values of J for this term? [3]
(b) Determine the energy shift arising from spin-orbit coupling for each
of the J sub-levels in terms of the spin-orbit coupling constant for
this atom, ASO . [2]
(c) By considering the J state multiplicity, show that the total energy
shift of the system is zero. [3]

1
3. The ionization potential of Li is 5.39 eV, the electron affinity of F is 3.45
eV, and the equilibrium internuclear distance in LiF molecule is 1.56
Å. Estimate the value of a dissociation energy of LiF. Explain why your
result differs from the experimental value of 5.9 eV.
[Note: 1 Hartree = 27.2 eV and a0 = 0.529 Å] [5]

4. The experimentally measured wave numbers of the first three pure ro-
tational transitions in the HD molecule are:

J = 0 → J′ = 1 89.228 cm−1
J = 1 → J′ = 2 177.842 cm−1
J = 2 → J′ = 3 265.241 cm−1

(a) Using this data determine the aver age value of the rotational con-
stant B. [3]
(b) Calculate the corresponding equilibrium internuclear distance Re .
[Note: mass of the deuterium atom MD = 2MH , where MH is the
mass of hydrogen atom]. [4]
(c) Assuming that the equilibrium internuclear distance in HD and that
in the more exotic isotopomer of the hydrogen molecule, HT (where
T represents the tritium atom with a mass MT = 3MH ) are equal,
what is the rotational constant of the ground state of HT? [3]
(d) Explain how you expect the intensities of the rotational transitions
in HD and HT to compare to those of rotational transitions in an
ionically bound molecule, such as LiF. [3]

2
Model Answers
1. (a) The 1s2s configuration in He has ℓ1 = 0, ℓ2 = 0, s1 = 1/2 and
s2 = 1/2.
Therefore

L = |ℓ1 − ℓ2 | · · · |ℓ1 + ℓ2 | = 0
S = |s1 − s2 | · · · |s1 + s2 | = 0 or 1
[2]

and the allowed terms are

1
S and 3 S
[2]

(b) i. The 3 S term lies at 159 855.97 cm−1 . [1]

1 −1
The S term lies at 166 277.44 cm . [1]

ii. The energy difference between these terms is a result of the

exchange interaction. [1]

iii. For the 3 S term with n = 2 the energy with respect to the ionisa-
tion limit is the difference between the term energy and ground
state ionisation energy, i.e.,

E23 S Eion
= 159 855.97 −
hc hc

= −38 454.70 cm−1

[1]

Therefore from the Rydberg formula

RHe
− = −38 454.70
(n − ∆23 S )2 [1]

when n = 2 and hence

(2 − ∆23 S ) = 1.689

3
and

∆23 S = 0.311.
[1]

In the case of the 1 S term

E21 S Eion
= 166 277.44 −
hc hc

= −32 033.23 cm−1

[1]

and consequently

(2 − ∆21 S ) = 1.851

and

∆21 S = 0.149.
[1]

4
2. (a) The Term 5 D has L = 2 and 2S+1 = 5, hence S = 2. [2]
The possible J values are given by

J = |L − S| · · · |L + S| = 0, 1, 2, 3, 4

[1]

(b) The energy shift ∆ESO due to spin-orbit coupling is given by [1]
 
∆ESO ASO
= J(J + 1) − L(L + 1) − S(S + 1)
hc 2

For all J terms -L(L+1)-S(S+1) = -12. Therefore the energy shifts

for each J sub level are

J = 0: ∆ESO = ASO /2 [0-12] = -6ASO

J = 1: ∆ESO = ASO /2 [2-12] = -5ASO
J = 2: ∆ESO = ASO /2 [6-12] = -3ASO
J = 3: ∆ESO = ASO /2 [12-12] = 0
J = 4: ∆ESO = ASO /2 [20-12] = 4ASO
[1]

(c) For every J state there are (2J+1) MJ substates. [1]

Therefore the total energy shift due to spin orbit coupling for a given
J is the shift multiplied by the number of substates:

∆E(J = 0)SO × (2J + 1) = -6A

∆E(J = 1)SO × (2J + 1) = -15A
∆E(J = 2)SO × (2J + 1) = -15A
∆E(J = 3)SO × (2J + 1) = 0
∆E(J = 4)SO × (2J + 1) = +36A

The sum of these is zero. [2]

5
3. The ionization potential of lithium is 5.39 eV, the electron affinity of F is 3.45 eV,
and the equilibrium internuclear separation of LiF molecule is 1.56 Å. Estimate
the value of a dissociation energy of LiF. Explain why your result differs from the
experimental value of 5.9 eV [Note: 1 Hartree = 27.2 eV and a 0 = 0.529 Å)

Answer:

The equilibrium distance is = 2.948 a.u.

Assuming ionic bonding and QLi = +1, in atomic units, the Coulomb attraction energy at
equilibrium internuclear separation is ✓

ECoulomb = 1/R = 1/2.948 = 0.339 a.u. = 9.22 eV ✓ [2]

The dissociation energy can be estimated as the value of the Coulomb attraction between ions
after the electron transfer minus the energy loss due to the electron transfer:

D.E. = ECoulomb – [I.P(Li) + E.A(F)] = 9.22 – (5.39 - 3.45) = 7.28 eV ✓ [1]

The calculated value significantly exceeds the experimental value because:

The effective charges on Li and F are less than +/- 1.0 assumed in the calculation. ✓ [1]

The estimate does not take into account the Pauli repulsion of electrons and the nuclear
repulsion, which stops ions from collapsing at short distances. ✓ [1]

4. The experimentally measured wave numbers of the first three pure rotational
transitions in the HD molecule are:

J = 0 → J’ = 1 89.228 cm -1
J = 1 → J’ = 2 177.842 cm -1
J = 2 → J’ = 3 265.241 cm -1

(a) Using this data determine the average value of the rotational constant B. [3]

(b) Calculate the corresponding equilibrium internuclear distance R e . (Note: mass of

the deuterium atom MD = 2MH, where MH = 1.673 x 10-27 kg is the mass of hydrogen
atom). [4]

(c) Assuming that the equilibrium internuclear distance in HD and that in the more
exotic isotopomer of the hydrogen molecule, HT (where T represents the tritium
atom with a mass MT = 3MH) are equal, what is the rotational constant of the ground
state of HT? [3]

(d) Explain how you expect the intensities of the rotational transitions in HD and HT
to compare to those of rotational transitions in an ionically bound molecule, such as
LiF. [3]
Correct answer: B = 44.427 cm -1

39.490 cm-1