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O F F I O F O F I F F O: Chem 64 PS 2 Solutions Problem 4.1. IF

This document discusses the molecular structures and symmetry of various compounds. Problem 4.1 discusses the trigonal bipyramidal structure of IF3O2 and its C2v isomer being the lowest energy structure. Problem 4.2 discusses degeneracy in symmetry and the non-degenerate vibrational modes of NH2D2+ compared to NH4+. Problems 5-7 use character tables and irreducible representations to determine the vibrational modes and infrared activity of molecules like VO4^3- and isomers of [Mn(CO)4Br2]-.

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99 views

O F F I O F O F I F F O: Chem 64 PS 2 Solutions Problem 4.1. IF

This document discusses the molecular structures and symmetry of various compounds. Problem 4.1 discusses the trigonal bipyramidal structure of IF3O2 and its C2v isomer being the lowest energy structure. Problem 4.2 discusses degeneracy in symmetry and the non-degenerate vibrational modes of NH2D2+ compared to NH4+. Problems 5-7 use character tables and irreducible representations to determine the vibrational modes and infrared activity of molecules like VO4^3- and isomers of [Mn(CO)4Br2]-.

Uploaded by

sara brito
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Chem 64 PS 2 Solutions

Problem 4.1. IF3O2 has 5 sets of electron pairs around the central I, so it will
have a trigonal bipyramidal structure. The possible isomers and their point
groups are in the box. Note that deviations from the ideal trigonal bipyramidal
angles in the first two structures do not alter the molecular symmetry.

F O O
O F F
O I F I F I
F O F
F F O
C 2v Cs D3h

From (advanced) VSEPR, the 2 electron pairs in the I=O double bond will take
more space/create more repulsions than the I-F bonding pairs, so they should be
in equatorial positions; moreover the more electronegative F atoms are expected
to be axial in the lowest-energy structure (C2v).
:

:F :
:

O:
: :

:F I
O:
:F :
:
:

Problem 4.2. “Degenerate” usually means “having the same energy”, as


frequently used to describe orbitals. When we are considering symmetry, it
indicates two or more objects that have the same symmetry (the same Mulliken
symbol represents their symmetry properties).
(a) For tetrahedral NH4+, the Td character table shows that the IR-active
vibrations (having x and/or y and/or z) symmetry are triply degenerate (T2).
(b) NH2D2+, however, has C2v symmetry (note: H and D are chemically
similar but with regard to vibrations they are different because of different mass).
In this point group, x, y, and z have different symmetries (B1, B2, and A1
respectively), so we can predict that the IR modes of NH2D2+ will have different
symmetries and be non-degenerate.

2. (a) D2h (b) C2v (c) linear, Dooh (d) square planar, D4h (e) D2d (f) D3 (g) C3v (h) D5h
(i) D5d

1
3. You can read these answers off the character tables

s pz px py dz2 dx2-y2 dxy dxz dyz


a D2h Ag B1u B3u B2u Ag Ag B1g B2g B3g
b C2v A1 A1 B1 B2 A1 A1 A2 B1 B2
c Dooh A1g A1u E1u E1u A1g E2g E2g E1g E1g
d D4h A1g A2u Eu Eu A1g B1g B2g Eg Eg
e D2d A1 B2 E E A1 B1 B2 E E
f D3 A1 A2 E E A1 E E E E
g C2h Ag Au Bu Bu Ag Ag Ag Bg Bg
h D5h A1' A2'' E1' E1' A1' E2' E2' E1'' E1''
i D5d A1g A2u E1u E1U A1g E2g E2g E1g E1g

Note: in some cases above a pair of orbitals transforms together with E


symmetry. This is indicated by the bold type (for example, in D4h, the px and py
orbitals together have Eu symmetry, and the dxz, dyz pair transform as Eg.)

4. i. D6h, ii. C2v, iii. C2v, iv. D2h, v. D3h, vi. C2v, vii. D2h, viii. D3h (trigonal bipyramidal)
or square pyramidal (C4v) ix. C3v, x. C2v and C2h, xi. Bent, Cs, xii. C2v and Dooh

5. molecular symmetry: C4v. Assign the basis function (V-O vector) to an


irreducible representation by determining how the vector is transformed by each
symmetry operation of the group:

C4v E 2C4 C2 2σV 2σd


V-O 1 1 1 1 1

This representation has A1 symmetry, so this is the symmetry of the V-O


stretching vibration.

6. (a) C6v: Γred = 2A2 + B1 + E1 +E2

(b) D2d: Γred = A2 + 2E

(c) Td: Γred = E + 2T2

2
7. There are 2 possible structures for [Mn(CO)4Br2]–, which have trans or cis
bromides:

- -
Br Br
OC CO OC CO
Mn Mn
OC Br OC CO
OC Br

cis C2v trans D4h


To calculate the number of CO stretching vibrations expected for each molecule,
use as a basis only the vectors directed along each C-O bond.

C2v E C2(z) σv(xz) σv(yz)


ΓCO 4 0 2 2

Reduce this representation to get ΓCO = 2a1 + b1 + b2


These have the following activity: 2a1 (IR/R)+ b1 (IR/R) + b2 (IR/R) so 4 peaks are
expected in the IR spectrum.

Do the same thing for the trans isomer in D4h: [Note that the C2' axis includes 2 of
the CO ligands, like σv, and the C2'' axis goes in between the ligands, like σd.]

D4h E 2C4(z) C2(z) 2C2' 2C2'' i 2S4(z) σh 2σv 2σd


ΓCO 4 0 0 2 0 0 0 4 2 0

This gives ΓCO = a1g (R) + b1g (R) + eu (IR) so only 1 peak is expected in the IR
spectrum.
Therefore, the isomer formed in the reaction must have the cis structure.

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