PC V: Spectroscopy Solution Exercise 4 FS 2021

Solution Exercise 4

Exercise 1: Molecular Structure of O2

a) For the construction of the molecular orbital (MO) scheme, it is sufficient to consider only
the atomic valence orbitals of the second shell, since the overlap of the inner shell atomic
orbitals (AOs) is usually too small to significantly contribute to the valence shell molecular
orbitals. The MOs arising from the 1s AOs are almost completely localized on the atoms
and have very low energies.
The MO scheme for O2 is shown in Figure 1-1. Note that the relative ordering of the
molecular orbital energies as depicted in Figure 1-1 is only valid for F2 and O2 . The ordering
is different for the other homo-nuclear diatomic molecules of the second row elements and it
is know as the s-p interaction. In these molecules, σg MO lies between the bonding πu and
the anti-bonding πg∗ MOs.

2p 2p

2s 2s

Figure 1-1: Molecular orbital scheme for O2 . The electron occupation is shown for the ground
state.

b) The two energetically lowest configurations (molecular orbital occupations) are:

lowest energy configuration: (1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (3σg )2 (1πu )4 (1πg∗ )2
first excited configuration: (1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (3σg )2 (1πu )3 (1πg∗ )3

c) An intuitive picture of how to place two electrons into two degenerate πg λ = −1 λ = 1 Λ

orbitals is given to the right. The two microstates yielding Λ=2 require ↑↓ 2
↑↓ 2
paired electrons, resulting in a 1 ∆g term. The four microstates with Λ=0
↑ ↑ 0
result in a 1 Σg and a 3 Σg state. The Pauli principle requires that the orbital ↑ ↓ 0
wave function of the singlet (triplet) term is symmetric (antisymmetric), ↓ ↑ 0
3 −
thus the full term labels are 1 Σ+ g and Σg . ↓ ↓ 0

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PC V: Spectroscopy Solution Exercise 4 FS 2021

The molecular term symbols for the first configuration are

(. . . ) (1πu )4 (1πg∗ )2 → 3 Σ− 1 1 +
g (paramagnetic), ∆g (paramagnetic), Σg (diamagnetic).

In the first excited configuration the two electrons are in different molecular orbital shells and
thus the Pauli principle does not impose any restriction on the symmetry of the wave function
(i.e. all combinations of symmetric and antisymmetric spatial and spin wave functions are
allowed):

(. . . ) (1πu )3 (1πg∗ )3 → 1 Σ− 3 3 +
u (diamagnetic), ∆u (paramagnetic), Σu (paramagnetic),
3
Σ− 1 1 +
u (paramagnetic), ∆u (paramagnetic), Σu (diamagnetic).

The ordering is with respect to the energy of the states. Hund’s rule can be applied for the
electronic states resulting from the most stable configuration. For states with the same spin
mulitplicity the term with the higher angular momentum quantum number |Λ| is lower in
energy. In case of the excited configuration Hund’s rule is no longer valid and therefore a
singlet state can be the energetically lowest state.
The magnetic properties of a term are most easily obtained by looking at the term symbol:
according to Herzberg [3], for light diatomic molecules the magnetic moment associated with
the total angular momentum of the electron around the internuclear axis is

µΩ = (Λ + 2Σ)µ0 , (1.1)

where µ0 is the Bohr magneton. For a 1 Σ state, µΩ always vanishes and thus the term is
diamagnetic. The 3 Σ and 1 ∆ terms can have non-zero values of µΩ and are thus paramag-
netic.

d) The ground state for O2 is the 3 Σ−

g state because it has the highest multiplicity.

e) The first transition is the one between the ground state and the first excited state (3 Σ− g →
1
∆g ). This transition occurs in the IR range of the electromagnetic spectrum and it is not
visible by eye. The higher energy transition is the one from the ground state to the second
singlet excited state (3 Σ− 1 +
g → Σg ). In this case, the transition occurs in the red visible/NIR
range of the electromagnetic spectrum. Therefore, the expected color is blue. Both the
transitions are forbidden because they violate the spin selection rule (∆S = −1) and the
LaPorte parity selection rule (g → g). Hence, they are not expected to occur in the gas
phase, where the molecules behave almost like isolated systems. The transitions weakly
appear in the condensed phase, where the molecules are no longer isolated systems and spin
flips are not strictly forbidden.

Exercise 2: Electronic Spectrum of N2

a) The molecular orbital (MO) scheme for N2 for the ground and excited configuration is shown
in Figure 2-1.

b) The energy for one transition is given by the difference between two vibrational levels of the
electronic ground and excited state. With the transition energy is
2 2
E(v 0 , v 00 )
     
0 00 0 0 1 0 0 0 1 00 00 1 00 00 00 1
= Te − Te + ωe v + − ωe xe v + − ωe v + + ωe xe v + .
hc 2 2 2 2
(2.1)

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PC V: Spectroscopy Solution Exercise 4 FS 2021

E E

2p 2p 2p 2p

2s 2s 2s 2s

a b

Figure 2-1: MO schemes for N2 . a shows the ground state and b the excited state.

For emission with v 0 = 0, the difference from consecutive levels v and v + 1 is

∆E(v) = E(v 0 = 0, v 00 = v) − E(v 0 = 0, v 00 = v + 1) = ωe00 − 2ωe00 x00e − 2ωe00 x00e v. (2.2)
A fit of this expression to the experimental data can be used to determine the vibrational
constants ωe00 and x00e of the electronic ground state. For the absorption with v 00 = 0 to the
consecutive levels v and v + 1,
∆E(v) = E(v 0 = v + 1, v 00 = 0) − E(v 0 = v, v 00 = 0) = ωe0 − 2ωe0 x0e − 2ωe0 x0e v. (2.3)
Fitting the parameters of these expression to the given data, one obtains the vibrational
constants for both electronic states. The literature value from Ref. [2] is given in brackets.
1
Σ+
g : ωe00 = 2358.5 (2358.57) cm−1 ωe00 x00e = 14.4 (14.324) cm−1
1
Πg : ωe0 = 1691.826 (1694.20) cm−1 ωe0 x0e = 13.633 (13.949) cm−1

c) The intensities are influenced by the population of the vibrational levels and by the overlap
of the vibrational wavefunctions (Franck–Condon factors).
d) As discussed above, the intensity of a transition in the absorption spectrum is determined
by the transition probability and by the population of the initial level. In a sample of light
molecules in thermal equilibrium at room temperature (or below), most molecules will be in
the v 00 = 0 level (Boltzmann factor). Thus one can expect a prominent progression in the
absorption from this level.
e) The plot of the absorption intensities in the exercise sheet reveals the typical pattern for
an excited state which has a different equilibrium bond length than the ground state. This
means that the potential energy curve of the excited state is shifted to longer or shorter
equilibrium bond lengths with respect to the ground state potential energy curve, as the
overlap between the vibrational wavefunctions of different electronic states (Franck–Condon
factors) must be smaller.
Typical vibrational progression intensity distributions for the two cases of almost equal and
significantly different equilibirium distances re are shown in Figure 2-2.

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PC V: Spectroscopy Solution Exercise 4 FS 2021
0 3

4 2

5
6 1
1 7
8 0
2

a b

Figure 2-2: Qualitative intensity distributions for the case where re0 = re00 (a) and the case
re0 > re00 (b)

Exercise 3: Rovibrational spectroscopy of HCl

a) The electronic ground state of HCl is a 1 Σ+ term. For diatomics the rotational selection
rule for transitions between states with Λ=0 (Σ states) is ∆J = J 0 − J 00 = ±1. We obtain
therefore a so-called P branch with ∆J = −1 and an R branch with ∆J = +1. The transition
wavenumbers ν̃ = T (v 0 , J 0 ) − T (v 00 , J 00 ) are given by
ν̃∆J (J) = T (v 0 , J + ∆J) − T (v 00 , J)
= G(v 0 ) − G(v 00 ) + B 0 (J + ∆J)(J + ∆J + 1) − B 00 J(J + 1)
− D0 (J + ∆J)2 (J + ∆J + 1)2 + D00 J 2 (J + 1)2 + . . . ,
ν̃P (J) = G(v 0 ) − G(v 00 ) + B 0 (J − 1)J − B 00 J(J + 1)
− D0 (J − 1)2 J 2 + D00 J 2 (J + 1)2 + . . . ,
= G(v 0 ) − G(v 00 ) + B 0 (−J)(−J + 1) − B 00 (−J)(−J − 1)
− D0 (−J)2 (−J + 1)2 + D00 (−J)2 (−J − 1)2 + . . . , (3.1)
ν̃R (J) = G(v 0 ) − G(v 00 ) + B 0 (J + 1)(J + 2) − B 00 (J + 1)J
− D0 (J + 1)2 (J + 2)2 + D00 (J + 1)2 (J)2 + . . . (3.2)
Eqs. (3.1) and (3.2) may be replaced by a single formula
ν̃(m) = G(v 0 ) − G(v 00 ) + B 0 m(m + 1) − B 00 m(m − 1)
− D0 m2 (m + 1)2 + D00 m2 (m − 1)2 + H 0 m3 (m + 1)3 − H 00 m3 (m − 1)3 + . . .
= ν̃0 + (B 0 + B 00 )m + (B 0 − B 00 + D00 − D0 )m2 + [−2(D0 + D00 ) + (H 0 + H 00 )]m3
+ [(D00 − D0 ) + 3(H 00 − H 0 ) + . . .]m4 + . . .
≈ ν̃0 + (B 0 + B 00 )m + (B 0 − B 00 )m2 − 4Dm3 (3.3)
where ν̃P (J) = ν̃(m=−J) and ν̃R (J) = ν̃(m=J +1). Note that there is no line for m = 0.
For vibrational transitions starting from v 00 = 0 we obtain
ν̃0 = G(v 0 ) − G(0) = v 0 ωe − v 0 (v 0 + 1)ωe xe ,
B 0 + B 00 = 2Be − (v 0 + 1)αe ,
B 0 − B 00 = −v 0 αe .
For the fundamental vibration we get
ν̃P (J) = ωe − 2ωe xe − 2Be J − αe J(J − 2) + 4DJ 3 ,
ν̃R (J) = ωe − 2ωe xe + 2Be (J + 1) − αe (J + 1)(J + 3) − 4D(J + 1)3
ν̃(m) = ωe − 2ωe xe + 2Be m − αe m(m + 2) − 4Dm3 .

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PC V: Spectroscopy Solution Exercise 4 FS 2021

The definitions for the first harmonic can be written down in full analogy. As the form
of Eq. (3.3) suggests, the spectroscopic constants can be obtained by fitting a polynomial
function to the observed transition wavenumbers.

b) The assignment of the transitions in the fundamental band are shown in table 3.1. The
transitions of the first harmonic can be assigned in full analogy, which is not shown explicitly.
The additional resonances appearing in the spectrum of the v 0 = 2 ← v 00 = 0 vibrational
band of HCl are due to the isotopolog H37 Cl.

Table 3.1: Assignment and experimental differences, second and third differences of the vibra-
tional band v 0 = 1 ← v 00 = 0.

J m ν̃(m)/ cm−1 ∆ν̃(m)/ cm−1 ∆2 ν̃(m)/ cm−1 ∆3 ν̃(m)/ cm−1

P(12) 12 −12 2599.03962 26.70536 −0.46434 −0.01054
P(11) 11 −11 2625.74498 26.24102 −0.47488 −0.01605
P(10) 10 −10 2651.98600 25.76614 −0.49093 −0.01156
P(9) 9 −9 2677.75214 25.27521 −0.50249 −0.01432
P(8) 8 −8 2703.02735 24.77272 −0.51681 −0.01346
P(7) 7 −7 2727.80007 24.25591 −0.53027 −0.01289
P(6) 6 −6 2752.05598 23.72564 −0.54316 −0.01289
P(5) 5 −5 2775.78162 23.18248 −0.55605 −0.01398
P(4) 4 −4 2798.96410 22.62643 −0.57003 −0.01351
P(3) 3 −3 2821.59053 22.05640 −0.58354
P(2) 2 −2 2843.64693 21.47286
P(1) 1 −1 2865.11979

R(0) 0 1 2906.27016 19.64891 −0.63174 −0.01431

R(1) 1 2 2925.91907 19.01717 −0.64605 −0.01086
R(2) 2 3 2944.93624 18.37112 −0.65691 −0.01115
R(3) 3 4 2963.30736 17.71421 −0.66806 −0.01239
R(4) 4 5 2981.02157 17.04615 −0.68045 −0.01060
R(5) 5 6 2998.06772 16.36570 −0.69105 −0.01217
R(6) 6 7 3014.43342 15.67465 −0.70322 −0.00972
R(7) 7 8 3030.10807 14.97143 −0.71294 −0.01223
R(8) 8 9 3045.07950 14.25849 −0.72517 −0.00881
R(9) 9 10 3059.33799 13.53332 −0.73398
R(10) 10 11 3072.87131 12.79934
R(11) 11 12 3085.67065

c) In the solution we will employ the method of combination differences. For the fundamental
one finds the following expressions for the combination differences:

∆ν̃P (J) = ν̃P (J + 1) − ν̃P (J) = −2Be − αe (2J − 1) + 4D(3J 2 + 3J + 1),

∆ν̃R (J) = ν̃R (J + 1) − ν̃R (J) = 2Be − αe (2J + 5) − 4D(3J 2 + 9J + 7),
∆2 ν̃P (J) = ∆ν̃P (J + 1) − ∆ν̃P (J) = −2αe + 24D(J + 1),
∆2 ν̃R (J) = ∆ν̃R (J + 1) − ∆ν̃R (J) = −2αe − 24D(J + 2),

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PC V: Spectroscopy Solution Exercise 4 FS 2021

or, when using Eq. (3.3),

∆ν̃(m) = ν̃(m + 1) − ν̃(m) = (B 0 + B 00 ) + 2(B 0 − B 00 )(2m + 1) − 4D(3m2 + 3m + 1)

= (2Be − 3αe − 4D) − (2αe + 12D)m − 12Dm2 ,
∆2 ν̃(m) = ∆ν̃(m + 1) − ∆ν̃(m) = 2(B 0 − B 00 ) − 24D(m + 1)
= −(2αe + 24D) − 24Dm,
∆ ν̃(m) = ∆2 ν̃(m + 1) − ∆2 ν̃(m) = −24D,
3

where ∆n ν̃P (J) = (−1)n ∆ν̃(m=−J −n) and ∆n ν̃R (J) = ∆n ν̃(m=J +1).
The average of the third differences ∆3 ν̃ in Table 3.1 yields D = 5.13 · 10−4 cm−1 , (the first
harmonic can be assigned in full analogy, which is not shown explicitly) from which the
other parameters can be deduced. A polynomial fit of third order (including also the first
harmonic v 0 = 2 ← v 00 = 0) yields
D = 5.200(33) · 10−4 cm−1 ,
αe = 0.30259(18) cm−1 ,
Be = 10.59108(57) cm−1 ,
ν̃01 = ωe − 2ωe xe = 2885.9838 cm−1 .

With the value ν̃02 = G(2) − G(0) = 2ωe − 6ωe xe = 5668.006(2) cm−1 we obtain
ωe = 3(G(1) − G(0)) − (G(2) − G(0)) = 2989.878(44) cm−1 and
ωe xe = (G(1) − G(0)) − (G(2) − G(0))/2 = 51.956(12) cm−1 .
Huber & Herzberg [2] give the following values: ωe = 2990.946 cm−1 , ωe xe = 52.8186 cm−1 ,
Be = 10.59341 cm−1 , αe = 0.30718 cm−1 , D = 5.3194 · 10−4 cm−1 .

d) The bond length of the H35 Cl molecule at equilibrium Re can be derived from the rotational
constant Be :
~
Be = with: I = µR2
4πcI
~
= (3.4)
4πcµRe2
−1
µ = (1.008 u)−1 + (34.9689 u)−1 = 1.62693 · 10−27 kg

(3.5)
s
h
Re = = 1.274584(3) · 10−10 m = 1.274584(3)Å (3.6)
8π 2 cµBe

References
[1] A. Lofthus, The Spectrum of Molecular Nitrogen, J. Phys. Chem. Ref. Data, 6(1) (1977)
113–307.

[2] K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, Vol. IV: Con-
stants of diatomic molecules, Van Nostrand Reinhold Company Inc. New York, 1979.

[3] G. Herzberg, Molecular Spectra and Molecular Structure, Vol. I: Spectra of diatomic
molecules, Krieger Publishing Company Inc. Malabar (Floria), 1989.

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