Spectroscopy

WBCH044-05
2022-2023
Room: Alette Jacobshal Exam Hall Exam Hall 1 K21 - O8
Wednesday 12 July 2023 08:30 - 10.30
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.

• 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. Photoelectric effect (5)

Describe the two main observations made in early studies of the photoelectric effect
and explain how these required the concept of quantisation to be explained. Use
diagrams where appropriate.

2. Wavepackets and wavefunctions (6)

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

(ii) zero-point energy

(iii) transition dipole moment

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 3. The wavefunction (8)
Consider a particle (mass is 9.5 × 10 −27
kg) moving along a line over which the
potential is constant. The particle is localized in the range 0 < x < L. This is
described by the Hamiltonian

ℏ2 ∂ 2
Ĥ = − + V̂
2m ∂x2

(i) show that ψ = e−ikx is an eigenfunction of Ĥ

(ii) calculate the eigenvalue in terms of k

(iii) Normalise this wavefunction between 0 and l

(iv) calculate the expectation value ⟨Hx ⟩

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2. Vibrational and rotational spectroscopy 18 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

Explain the various factors that contribute to determining the intensity and shape
of electronic absorption bands. In your answer consider symmetry and the nature
(e.g., π∗ ← π, dd transitions etc) of the transition in the context of the transition
dipole moment.

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 2. Normal modes (7)
The reducible representation (Γ) of chloroform (CH3 Cl) is 4A1 +A2 + 5E . It is in
the C3v point group

(i) How many vibrational (normal) modes does chloroform have?

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

(iii) Draw 6 of the normal modes (indicate if there is degeneracy) 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) Indicate above (with brief justification by reference to the character table) which
normal modes are IR active and which are Raman active.

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 3. Tumbling around (5)
(a) Estimate the most populated rotational level of 79
Br2 at 40 ◦ C? Take B = 15
GHz.

(b) Calculate the moment of inertia (I) for (i) 79 Br2 and (ii) 81 Br2 . The bond length
of 79
Br2 is 228 pm.

(c) The bond length of 79

Br2 is 228 pm. do you expect the bond length of 81
Br2 to
be longer or shorter? justify your answer

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3. Electronic states and spectroscopy 25 points

1. UV/vis absorption spectroscopy (4)

420 nm light was passed through 100 microns of an aqueous solution of a yellow
dye. A transmittance of 29.5% was noted. The molar absorbtivity is 250 M−1 cm−1 .
Calculate the absorbance and concentration of the dye.

2. Selection rules (6)

For the strong field complex [Fe(CN)6 ] 4–
use the Tanabe-Sugano diagram to:
i) indicate the ground state term
ii) indicate the spin-allowed transitions (draw clearly).

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 3. Microstates (7)
The Silicon atom can have an excited state electron configuration of [Ne]3s 3d .
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)

(i) X-ray fluorescence spectroscopy is used for rapid analysis of materials (e.g. using
a hand held device in a mine). Explain, considering electronic shells the process
by which X-ray emission is generated and why it gives element specific signals.

(ii) X-ray absorption spectroscopy is a useful technique to examine solid materials.

Explain the shape of the spectra shown below for solids containing iron. Justify
your answer.

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4. NMR theory 15 points

1. Larmor frequency (4)

What is the Larmor (precession) frequency of a 19
F NMR spectrum recorded on a
spectrometer with a 2.5 T magnetic field? What is the spin polarisation (p) at 35
◦
C?

2. Coupling (6)
Consider the first order spectrum of an AMX spin system with resonances shifted
by νA = 160, νm = 580 Hz and νx = 980 Hz from TMS (500 MHz spectrometer)
and JAM = 5, JAX = 20, JMX = 15. Is 1st order analysis justified? Assuming it is
sketch the "splitting diagrams" and indicate the relative magnitude of the signals
expected. Directly below, sketch the expected signals.

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 3. Chemical shift (5)
Explain, using diagrams and considering currents induced by the applied magnetic
field of an NMR spectrometer, why the 1 H signal of a terminal alkyne is at lower
ppm than that of ethene.

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5. Interpretation of spectra 23 points

1. Vibrational spectroscopyThe FTIR spectra of the following compounds are (5)

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

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 2. Spectral prediction (9)
Predict (sketch) the H (in box below) and
1 19
F (don’t worry about chemical shift,
only draw signal pattern) NMR spectra of propyl 2-fluoroacetate (shown below) with
expected chemical shift and coupling pattern/integration. Justify your prediction
briefly.

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 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 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

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