,

Spectroscopy
WBCH044-05
2021/22
Room Alette Jacobshal Exam Hall 1 A1 - H12
Tuesday 14 June 2022 12:15 - 14:15
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 question sets each of 20 pts. Total points: 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 Light and Quantum mechanics 20 pts
1. Describe in what way a molecule interacts with light with: (4)

1. a frequency of 300 GHz

2. a wavenumber of 24 000 cm−1

Justify your answers.

2. The diagrams below show the wavefunctions for two states of a particle in a one (2)
dimensional space. Indicate which state has highest kinetic energy. Explain your
reasoning clearly.

Faculty of Science and Engineering, RUG 2

 3. Explain briefly what is meant by the terms: (3)

1. Induced dipole moment

2. Bohr resonance condition
3. Orthogonal wavefunctions

4. Explain briefly (use diagrams where appropriate) (i) why Einstein’s interpretation (5)
of the photoelectric effect implies quantisation of the energy of photons and (ii) the
significance of the slope in the plot of kinetic energy of electrons versus wavelength

Faculty of Science and Engineering, RUG 3

 5. Normalise the following wavefunction ϕ = exp(iml x) where ml = 0, ±1, ±2, .. and show (6)
whether or not it is an eigenfunction of the operator for angular momentum for
̵ d
h
rotation in a plane (L̂z = i dϕ ) which delivers an eigenvalue.

Faculty of Science and Engineering, RUG 4

2 Electronic spectroscopy and term symbols 20 pts

Electronic absorption spectroscopy

1. The UV/Vis absorption spectrum of a solution of an Fe(IV) complex in water shows (4)
a weak band at 710 nm with a molar absorptivity of 350 M−1 cm−1 . What is the
transmittance of a 0.15 mmol dm−3 solution in a 1 mm pathlength cuvette at 710
nm. Show dimensional analysis clearly.

2. Order the 4 microstates shown below from lowest to highest energy, and if states are (4)
degenerate explain why. Justify your answer and calculate the spin multiplicity in
each case.

3. For the term symbols 4 G 3 , 4 F 3 , 6 S 1 (3)

2 2 2

1. Calculate the total number of microstates described by each term symbol

2. Determine whether or not the J value indicated is possible
3. indicate if transitions between each of the states and the others are allowed or
forbidden

In each case justify your answer briefly.

Faculty of Science and Engineering, RUG 5

 4. X-ray Photo-electron spectroscopy (XPS) uses X-rays to probe the electronic prop- (6)
erties of a material. Explain

• which orbitals are probed?

• which detection method is used
• why the sample has to be held under a strong vacuum

5. Explain the different X-ray absorption and emission processes taking place in an (3)
atom/molecule (to obtain an X ray Absorption Spectrum).

Faculty of Science and Engineering, RUG 6

3 Vibrational and rotational spectroscopy 20 pts
1. Explain what is meant by the term ’transition dipole moment’ in regard to vibrational (2)
spectroscopy.

2. The iron complex trans-[FeCl4 Br2 ] has approximately D4H symmetry. The small (6)
arrows in the figure below indicate the motion of atoms during one half cycle of a
mode. The symmetry species for the modes are in random order A1g , A2g , B1g , A2g

1. Use the appropriate character table and match each mode (a to d) to the correct
symmetry species. In each case, justify your answer clearly.
2. Which of the four modes is not a vibration (normal mode). Justify your answer.
3. For those modes that are vibrations, indicate with justification (using the charac-
ter table AND the change in dipole moment/polarizability during the vibration)
whether or not they are IR and/or Raman active.

Faculty of Science and Engineering, RUG 7

 3. Consider the small molecule NO. (6)

1. Estimate the most populated rotational level of 15 N17 O at (i) -25 and (ii) 205
°C? Take B = 37.636 GHz.
2. Sketch the expected rotational absorption spectrum of 15 N17 O at 205
3. indicate the gap between successive lines in terms of B
4. indicate the approximate relative intensity of the lines
5. identify the line of maximum intensity at 205 K.

Justify your answers and show workings clearly in each case.

4. Predict the (a) FTIR, (b) Raman spectra of H2 , HD and D2 (including number and (6)
relative intensity of bands as well as band position). Justify your prediction briefly.
Note that the force constant is ca. 576 N m−1

Faculty of Science and Engineering, RUG 8

4 NMR spectroscopy 20 pts

In your answers, you must show units and dimensional analysis clearly
NMR theory

1. What is the Larmor (precession) frequency of a 31 P nucleus in a 6.25 T magnetic (2)

field?

2. Calculate the magnitude of the spin angular momentum vector (|I|) for a 7 Li nucleus. (2)

3. The polarisation, p, of 1 H nuclei in a magnetic field at 400 K is 0.0000012. What (3)

is the Larmor frequency for a 1H nuclei in this magnetic field? What temperature
would be required to have the same polarisation using a 300 MHz spectrometer?

Faculty of Science and Engineering, RUG 9

 NMR coupling and splitting

4. Explain briefly the mechanism by which scalar coupling between NMR active nuclei (5)
occurs and how it leads to the coupling patterns observed (also briefly).

Spectral prediction

5. Predict the (a) 1 H NMR, (b) 13 C NMR spectra and (c) mass spectrum of 4-bromo- (8)
benyzlalcohol. Justify your prediction briefly.

Faculty of Science and Engineering, RUG 10

5 Spectral prediction and Interpretation 20 pts

FTIR spectroscopy

1. The FTIR spectra of the following compounds are shown below. (5)

i. Ethylene glycol (HOCH2 CH2 OH)

ii. Ethyl acetate (CH3 C(O)OCH2 CH3 )
iii. Dichloromethane (CH2 Cl2 )
iv. Acetonitrile (CH3 CN)
v. Toluene (C6 H5 CH3 )

In each spectrum label (up to 3) bands corresponding to major functional groups and
match the spectra to the structures; you must justify your answer briefly showing
reasoning.

Faculty of Science and Engineering, RUG 11

 Structure determination - 15 pts

Faculty of Science and Engineering, RUG 12

Faculty of Science and Engineering, RUG 13
 2. In the following problem try to identify as many spectral features as you can and if (15)
possible work out the structure.

• Label the signals shown in the expansion (inset) as singlet (s), doublet (d),
triplet (t), doublet of doublets (dd) etc.
• Identify which protons are coupling with each other
• Determine the ratio of hydrogens corresponding to each resonance
• Identify the solvent signals in the NMR spectra (or where it should be if you
can’t see it easily).
• Identify the bands in the FTIR spectrum that correspond to functional groups
present in the compound.
• Identify primary, secondary, tertiary, and Quaternary carbons.
• Identify halogen isotopes in the mass spectrum.
• Use the fragmentation pattern to identify structural fragments.
• Correlate the total mass with molecular formula.
• What does the UV-Vis spectrum give for information about the structure.
• Link the information from different techniques together
• Propose a structure that is consistent with the spectrum and the molecular
formula. Show which signal corresponds to which H in your structure

Faculty of Science and Engineering, RUG 14

Faculty of Science and Engineering, RUG 15
 blank 1

Faculty of Science and Engineering, RUG 16

 blank 2

Faculty of Science and Engineering, RUG 17