Spectroscopy

WBCH044-05
2022-2023
Room: Alette Jacobshal Exam Hall Exam Hall 1 D28 - L8
Wednesday 21 June 2022 15:00 - 17.00
Lecturers: Moniek Tromp, Tjalling Canrinus, Wesley Browne

• If you require additional paper to answer the questions, then use one of the blank
pages at the end of the exam. Write your name and question number on that
page. Note that all material submitted (including rough work) will be marked.
For rough work use the last two blank pages

• All material MUST be handed in before leaving the exam

• Use black or blue ink only (do not use pencil or other colours)

• Answers must be accompanied by appropriate dimensional analysis in order to be

deemed correct

• There are 5 parts to the exam, with each equal weight.

• Total points for the exam: 100

• The grade is determined by division of the total number of points by 10, followed
by rounding to the nearest half decimal

• Their are two blank pages at the end of the exam for additional space if needed.
Refer to their use at the question.

Name:

S-number:
1. Quantum concepts 19 points

1. Born interpretation of the wavefunction (5)

The Born interpretation of the wavefunction is that |ϕ| dx is the probability of find-
2

ing a particle in the range between x and dx. Give five requirements a wavefunction
must meet to be a proper wavefunction to describe the position and momentum of
a particle. Use diagrams where appropriate.

2. Wavepackets and wavefunctions (6)

Explain briefly, using diagrams where appropriate, what is meant by terms
(i) wavepacket

(ii) polarisability

(iii) orthogonality (in regard to wavefunctions)

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 3. The wavefunction (8)
Consider the angular momentum operator for a particle circulating a point on the
xy plane, where ϕ is the angle with respect to the x axis.

ˆl = −iℏ ∂
∂ϕ

(i) show that ψ = ei(kϕ) is an eigenfunction

(ii) calculate the eigenvalue
(iii) Normalise this wavefunction between 0 and 2π
(iv) calculate the expectation value ⟨l⟩

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2. Vibrational and rotational spectroscopy 19 points

1. Transition dipole moment (6)

The intensity of a spectroscopic signal is proportional to the square of the transition
dipole moment. The transition dipole moment can be calculated using the equation:
Z
µT M = ψf∗ µ̂ψi dτ

Compare and contrast the dipole moment µ̂ operator for Infrared absorption and
Raman scattering. Consider how the operator is replaced by a Talyor series and
how terms are eliminated to simplify it.Taylor expansion

1 d2 µ 1 d3 µ
     
dµ 2
µ̂ = µ0 + x+ 2
x + 3
x3
dx 0 2 dx 0 6 dx 0

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 2. Normal modes (8)
The reducible representation (Γ) of thioformaldehyde (CH2 S)is 4A1 + A2 + 3B1 +
4B2 . It is in the C2v point group

(i) How many vibrational modes does thioformaldehyde possess?

(ii) remove the symmetry species due to rotation and translation to give irreducible
representation for normal modes

(iii) Draw these normal modes using small arrows to indicate the direction of motion
in the plane of the page and + and – for motion out of the plane of the page
(yz)

(iv) Inidicate above (with brief justification) which normal modes are IR active and
which are Raman active.
(v) Identify, show justification, whether or not the electronic transition σ ∗ ← π is
symmetry allowed of forbidden for absorbtion of light polarised in the z direc-
tion.
(vi) If forbidden indicate which vibrational mode will make it allowed and what
polarisation of light is required.

Figure 1: MO diagram CH2 S

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 3. Tumbling around (5)
(a) Estimate the most populated rotational level of 2 H2 at -20 ◦ C? Take B = 450
GHz.

(b) Calculate the moment of inertia (I) for (a) 1 H2 and (b) 2 H2 . The bond lengths
are 106.9 pm and 105.5 pm, respectively.

(c) Why is the bond length for 2 H2 shorter than that of 1 H2 .

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3. Electronic states and spectroscopy 24 points

1. UV/vis absorption spectroscopy (4)

520 nm light was passed through 0.5 dm of an aqueous solution of a blue dye at shows
a transmittance of 19.5%. The molar absorbtivity is 1500 M−1 cm−1 . Calculate the
absorbance and concentration of the dye.

2. Selection rules (6)

Classify each of following atomic transitions as being allowed or forbidden. In the
case that a transition is forbidden, indicate which selection rule has been violated.
(i) 4 F 5 → 2 D 3
2 2

(ii) P 3 → G 5
2 2
2 2

(iii) 4 P 1 → 4 F 1
2 2

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 3. Microstates (6)
The Silicon atom has an electron configuration of [Ne]3s 3p .
2 2

(a) Determine the term symbols of Silicon (hint! by drawing the minimum required
number of microstates necessary).
(b) Determine, with brief justification, which term symbol corresponds to the ground
(lowest energy) microstate.

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 4. X-ray spectroscopy (8)
X-ray spectroscopy is a useful technique to examine solid materials.
Discuss how X-rays used in X-ray Spectroscopy are generated.
(i) What methods are available for generating X-rays - describe briefly how they
work?

(ii) Why are X-rays called X-rays?

(iii) Why are the shells labelled K, L, M... etc?

(iv) Explain briefly how photoelectron spectroscopy is carried out/performed and

in your answer comment on why a good vacuum is needed.

(v) In figure 2 below explain why two signals are observed for the 4f peak of gold

Figure 2: 4f part of the XPS spectrum of gold

Spectroscopy exam Page 9 of 17

4. NMR theory 15 points

1. Larmor frequency (4)

What is the Larmor (precession) frequency of a Li NMR spectrum recorded on a
7

spectrometer with a 6.3 T magnetic field? What is the spin polarisation (p) at 25
◦
C?

2. Angular momentum (6)

The spin angular momentum of Fe is 9.132×10
57 −35
J s and γ = 1.38×10 radT
6
s .
−1 −1

Determine
(a) the spin quantum number
(b) magnetic moment vector (|µ|)
(c) the z-component of the magnetic moment vector(µz )?

Spectroscopy exam Page 10 of 17

 3. Scalar coupling (5)
Explain, using diagrams, the mechanism by which scalar coupling arises in NMR
spectra, e.g. use 1 H-12 C-12 C-1 H as an example, considering the various interactions
between nuclear spins and electrons.

Spectroscopy exam Page 11 of 17

5. Interpretation of spectra 23 points

1. Vibrational spectroscopyThe Raman spectra of the following compounds are (7)

shown below. Label significant bands corresponding to functional groups and match
the spectra to the structures;

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 2. Spectral prediction (7)
Predict (sketch) the H NMR spectrum of para-ethoxy-stilbene (shown below) with
1

expected chemical shift and coupling pattern/integration. Justify your prediction

briefly.

Spectroscopy exam Page 13 of 17

 3. Structure determinationIn the following problem try to identify as many spec- (9)
tral features as you can and if possible work out the structure. Only answers given
on the problem will be graded; a list of points on a separate page will not be
accepted
• Label the signals shown in the expansion as singlet (s), doublet (d), triplet (t),
doublet of doublets (dd) etc.
• Identify which protons are coupling with which other protons
• Determine the relative ratio of hydrogen atoms corresponding to each resonance
• Identify the solvent signal in the 13
C NMR spectra (justify your answer).
• Identify the bands in the FTIR spectrum that correspond to functional groups
present in the compound.
• Identify the m/z signals in the mass spectrum and corresponding ions.
• comment on the significance of the absorption spectrum.
• Propose a structure that is consistent with the spectrum and the molecular
formula. Show which signal corresponds to which H in your structure

Spectroscopy exam Page 14 of 17

 IR Spectrum
(liquid film)

4000 3000 2000 1600 1200 800 0.0

V (cm· 1 )

100 Mass Spectrum

91 0.5 Q)
g
80 .,-:
"'
Q)
a. ~
60 Q)
V, .2
40
"'
.0
0
1.0 "' UV spectrum
~ 5.30 mg I 10 mis'
M+·
20 198/200 path length : 1.00 cm
solvent : cyclohexane

40 80 120 160 200 240 280 200 · 250 300 350

mle II, (nm)

,._ Resolves into

13 c NMR Spectrum two signals at higher field
(50.0 MHz, CDCl 3 solution)

- - Resolves into
two signals at higher field
7f'
expans~

proton decoupled solvent ppm

35.0 34.0

200 160 120 80 40 O o(ppm)

1H NMR Spectrum expansion

(200 MHz, CDCl 3 solution)

3.0 2.5 ppm

TMS

10 9 8 7 6 5 4 3 2 1 0
o(ppm)
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 blank 2

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