Spectroscopy

Code: 102531

II. VIBRATIONAL SPECTROSCOPY

1. The infrared spectrum of HI shows a fundamental vibrational band at 2230 cm-1.

Determine: (a) the fundamental vibrational frequency, in s-1, (b) the bond force
constant and (c) the zero-point energy, assuming that this molecule behaves like a
harmonic oscillator.

2. Determine the proportion of CO molecules present in the vibrational level = 1

with respect to those in level = 0, supposing that there is thermal equilibrium, at
temperatures of 500 K, 750 K and 1000 K. The fundamental vibrational frequency
is 2143 cm-1.

3. The 14N16O molecule has an intense absorption band at 1876.06 cm-1 and a weak
one at 3724.20 cm-1 ascribed to the first overtone. Use this data to find out the bond
force constant, the vibrational frequency and anharmonicity constant. How much is
the zero-point energy? Using the formula for the vibrational levels, estimate the
value of the dissociation energy of the molecule.

4. The spectrum of 1H19F presents an intense line at 3961.64 cm-1, and the equilibrium
vibrational frequency is 4138.52 cm-1. Determine the dissociation energy of 1H19F.

5. The fundamental harmonic frequency of 12C16O has been obtained from quantum
mechanical calculations and is 2202.6 cm-1. The anharmonicity constant obtained
through the same procedure is 4.48x10-3. Answer the following questions:
a) What is the value of the zero-point energy (ZPE)?
b) Compute the frequencies at which the fundamental band and the first overtone
will be seen.
c) What values would the same absorption bands have for the isotopologue 12C18O?
Data: Atomic masses: 12C = 12.000 amu, 16O = 15.995 amu.

6. The harmonic frequencies ̅ of 12C16O and 1H35Cl are 2202 and 2939 cm-1,
respectively. Their respective anharmonicity constants are 0.005 and 0.02. With
these data, and whenever necessary using their atomic masses approximated to be
integer, answer the following questions:
a) Find the values of the force constants of both molecules.
b) Estimate the vibrational level at which the dissociation will occur for both
molecules (Hint: in the anharmonic oscillator model, energy levels get closer
as the quantum number grows until they become degenerate. Thus, the
dissociation level can be estimated as the level where two consecutive states
 have the same energy, or in other words, the transition diss + 1 ← diss has
zero energy).
c) Estimate now the chemical dissociation energy of both molecules, .
d) Now, use your results concerning force constants, dissociative state number
and dissociation energy to discuss which of the two molecules has the
strongest bond. Do all results agree? Do you have any chemical information on
the structure that agrees, or disagrees, with your conclusion?

7. The vibrational frequency of the HF molecule is 4136 cm–1. At 25 ºC the most

intense transition on the R band is the 3 ← 2 transition, and the least intense that is
still observed is the transition 8 ← 7.

a) Draw a schematic representation of the ro-vibrational spectrum of this

molecule. Mark on the plot what lines correspond to the P and R branches,
along with their frequencies.
b) What is the most intense P line?
Data: = 18.3 cm-1 , = 17.5 cm-1

8. Find the symmetry elements of the following species and determine the point group
to which they belong.

1) WF5Cl 2) SF4
3) SiH3(CN) 4) PF5
5) 1-chloro-3,5-difluorobenzene 6) cis-[PtCl2(NH3)2]
7) trans-[PtCl2(NH3)2]

9. Find the symmetry elements and the point group of the main conformers of
butadiene.

10. Using ethylene oxide (C2H4O) as a test molecule, determine the multiplication table
for group C2v:
C2v E C2(z) σv(xz) σv’(yz) First operation

E
z
C2(z) O
x
σv(xz) C C
H H
H H
σv’(yz)

Second operation
a) Are all H atoms equivalent in C2H4O?
b) According to the table, is this group commutative (Abelian)?
11. Consider the character table for C4v (below, on the left). Check that the
corresponding direct product table (on the right) is correct and fill in the missing
representations:
C4v E 2C4 C2 2σv 2σv’ C4v A1 A2 B1 B2 E

A1 1 1 1 1 1 A1 A1 A2 ? ? ?

A2 1 1 1 –1 –1 A2 A2 ? B2 ? E

B1 1 –1 1 1 –1 B1 ? B2 A1 ? E

B2 1 –1 1 –1 1 B2 B2 ? A2 ? ?

E 2 0 –2 0 0 E ? E E ? A1+A2+B1+B2

a) In terms of Γ x Γ direct products: what can be said about the first representation
in all character tables (in this example A1)?
b) What can be said about the diagonal elements of the direct product table? (e.g.
B1xB1= A1)

12. The formaldehyde molecule (H2CO) has a total of six normal modes of vibration
with the following frequencies:

, / cm-1 1215 1281 1547 1861 2909 2969

Produce a list of all lines, irrespective of their intensities, that would be observed if
strong IR radiation were used to analyze the vibrational spectrum of formaldehyde
via absorption, and identify the transitions, classifying them as overtones,
combination bands and fundamental bands. Assume that your radiation source
spans the range between 100–3000 cm-1. Can you predict, based on what you know,
what the fundamental frequencies would be for D2CO?

13. Again for the formaldehyde molecule: do a symmetry analysis to find out the
symmetry species of all the normal modes (hint: start off the Γ ). Find now the
symmetry species of the C—H stretchings. Can you propose, based on the
symmetry of the latter, what form might these stretchings take?

14. The chromate anion can act as a counterion and as a mono- and bidentate ligand. In
the two latter cases it forms, in fact, polynuclear complexes, for instance:

K2CrO4 [Cr(CrO4)(NH3)5]NO3 [Cr(CrO4)(NH3)4]ClO4

 a) Determine, in each of the above cases,
the number of allowed bands that are
associated to the stretching vibrations
(Cr—O).
b) On the right, the spectra (a,
( b, c) of three
species containing the chromate ion are
represented (in particular, the region
where the stretching Cr—O
Cr vibrations
appear is shown). Work out the
behavior, as concerns coordination
mode, of the chromate ion in each case.

15. The IR spectrum of complex salt

[NEt4][MnI2(CO)4] presents, in CH2Cl2
solution, four bands in the region where
the CO stretching vibrations do normally
occur (roughly around 2000 cm-1). What
can be deduced about the structure of the
complex?x? (Hint: think of the possible
environment variations of the manganese
and work out the symmetry of the CO
stretchings in the corresponding
symmetry point group(s))

16. The figure shows the region of the IR spectrum

associated to the stretchings of the sulphate
sul
anion for three Co(III) complexes that contain it.
The
he frequencies of the vibrational modes of
SO42- as a free ligand are: ν(A1)=983 cm-1, ν
(E)=450 cm-1, ν (T T2)=1105 cm-1 and ν (T2)=611
-1
cm . Relate each of the spectra (solid line,
dot-dashed
dashed line and dotted line) with the
structure of the corresponding complexes.
17. The vibrational IR and Raman spectra of ethylene oxide present the following
bands between 1000 cm-1 and 4000 cm-1:
1120
IR 3079 - 3019 3005 1490 1470 - 1270 1153 1143
1120
Raman 3080 3063
63 3020 3005 1490 1470 1345 1266 1150 1140
Indicate the frequencies and symmetries of the vibrational modes ν(C—H). Try to
assign the bands at 3063 cm-1 and 3005 cm-1. (Hint: again, start working out the
symmetry of the C—HC H stretches. You might have to make assumptions based on
the likely value range
nge of the C—H
C stretching frequencies).

18. Consider the following four out-of-plane

out
motions of XeF4 (square planar) represented by
the vectors shown on the figure. Answer the
following questions:

a) Which symmetry species do these motions

belong to?
b) Two of thee motions shown are global
rotations of the whole molecule. Identify
them by means of their symmetry species
and the character tables and comment briefly on their relative energy.
c) Two of the shown motions are out-of-plane
out bending vibrations. Identify them.
d) Which of the two bending vibrations will be observed
observed in the IR spectrum?
e) Which of the two bending vibrations will be observed
observed in the Raman spectrum?

19. The IR spectrum of [Os(NH3)4(N2)2]2+, I,, is shown in Figure A, and those of dimers II
and III are shown inn Figure B (see below).

(I)

(II) (III)
 Figure A (IR spectrum) Figure B (IR spectrum)

Answer the following questions:

a) Determine the point group of the four Os complexes depicted above.
b) Based on the appearance of the N≡N stretching region (≈ 2000 cm-1) shown in the
IR spectrum in Figure A: Is complex I cis or trans? How many bands would you
expect in that region for the vibrational Raman spectrum of both cis and trans
isomers of complex I? Reason your answers by means of group theory.
c) Focus now on Figure B and assign each of the superimposed spectra (dashed and
solid lines) to one of the dinuclear species II or III. In order to do that, consider
the N≡N stretching region (≈ 2000 cm-1) in terms of local symmetry (local
symmetry means just considering the whole surroundings of the N≡ N bond as a
“superatom”, i.e. your molecule is now of the type X—NN—Y (with X and Y
taken as structureless atoms). Reason your assignment by means of group theory.
d) Would vibrational Raman spectroscopy based on the same N≡N stretching region
also be a good tool to discern between complexes II and III? Reason your answer
by means of group theory.
e) Compare the stretching frequencies of N2 when acting as terminal and bridging
ligand. Theorize about the origin of the differences.