5.

03 Exam 1
Christopher C. Cummins
February 18, 2011

Instructions

Clearly write your name at the top of this front page. Check your exam document to
make sure you have all 8 pages. This examination is closed-book and no calculators or
electronic devices may be employed. There are four multi-part questions; each part of each
question will be given equal weight for scoring purposes. Read all questions carefully before
writing down any answers. Enjoy the material!

1
Inorganic Chemistry 2

1. Write down the corresponding Schoenflies symbol (point group label) next to the pic-
ture of each molecule shown below. The point group flowchart is provided on the next
page.

(a) Square planar XeF4 .

(b) Planar B(OH)3 in the conformation shown.

(c) C60 , also known as Buckminsterfullerene.

(d) Ferrocene, Fe(η 5 -C5 H5 )2 , in the depicted staggered conformation.

Inorganic Chemistry 3

(e) Hydrogen peroxide, H2 O2 , in the depicted conformation.

Structure Yes D h

linear
linear Yes i

Special Group
Elements
No C v

8
Linear or Yes
low symmetry
Yes Cs

single element
Yes Ci
No
i
No C1

icosahedral
Yes Ih
highly symmetric
Sure? More than one Yes Yes
(octahedral, 6C5 i
Yes Cn axis of C3
tetrahedral,
or higher? No I
icosahedral)
No

High Symmetry
Yes Oh

octahedral

Elements
No 3C4 Yes i
No O
No

Yes Td
3S4 Tetrahedral
Yes Th
No
i
No T

Normal Yes Yes Yes Dnh

symmetry C2 Cn
Elements (most common)
Dihedral

Yes Dnd
Normal Symmetry

No
No
No Dn

Yes
Cnh
Single Axis

No
Yes
v Cnv

No
Yes S 2n
S2n
No Cn
Inorganic Chemistry 4

2. This question pertains to the normal mode vibrations for the ammonia molecule, NH3 .
The C3v character table is provided.

(a) Give a list of the set of characters that would be required as input to RE-
DUCE.EXE in order to obtain the Mulliken symbols for the irreducible repre-
sentations of the C3v point group corresponding to the normal mode vibrations
of NH3 .

(b) The normal modes for ammonia are found to transform as follows: 2A1 + 2E.
How many bands are expected in the infrared spectrum of NH3 ?

(c) How many bands are expected in the Raman spectrum of NH3 ?

(d) How many degrees of freedom does ammonia possess, altogether?

Inorganic Chemistry 5

(e) Write down the Mulliken symbols that correspond to translations and rotations
for NH3 .

(f) The infrared spectrum of ammonia is shown below. What is the approximate
energy range for the N–H stretching vibrations?

(g) Sketch the ammonia molecule and use vectors to represent atom motions for a
stretching vibration having A1 symmetry.
Inorganic Chemistry 6

3. This question pertains to the Berry Pseudorotation (BPR).

(a) What is the point group for the structure of SF4 at the transition state for BPR?

(b) How many of the atoms in SF4 are moving in the course of a single BPR event?

(c) By how many degrees does the SF4 molecule appear to have rotated after a single
BPR event?

19
(d) Is a single BPR event sufficient to exchange all the F environments for the SF4
molecule?

(e) If the 19 F NMR spectrum of SF4 were recorded at a very low temperature such
that the BPR process was essentially stopped (frozen, static structure), then how
many lines would be expected in the 19 F NMR spectrum, and what should be the
ratio of their intensities?
Inorganic Chemistry 7

4. Above are pictured in ascending order according to energy a grouping of the molecular
orbitals of B2 H6 . The grouping includes only the chemically significant valence orbitals;
core orbitals are not included. The choice of Cartesian axes is such that the terminal
hydrogens reside in the yz plane.
Inorganic Chemistry 8

(a) Using the character table for D2h (provided above), assign each of the pictured
molecular orbitals to its correct irreducible representation, and write the corre-
sponding Mulliken symbol above, next to each orbital’s picture.
(b) Next to the picture of the highest energy occupied molecular orbital for B2 H6 ,
write “HOMO”.
(c) Next to the picture of the lowest energy unoccupied molecular orbital for B2 H6 ,
write “LUMO”.
(d) Draw a circle around the MO that both has lots of boron 2s character and belongs
to the totally symmetric representation of the D2h point group.
(e) Draw a square around the pictured MO that involves overlap of boron px atomic
orbitals with s orbitals from the bridging hydrogens.