Chapter 6

Answers to Problems

6.1 (a) NH3

C3v E 2C3 3Fv

Ni 4 1 2
Pi 3 0 1
'3n 12 0 2

'3n = 3A1 + A2 + 4E
'trans = A1 + E 'rot = A2 + E
'3n-6 = 2A1 + 2E = 4 frequencies

Infrared 4 (2A1 + 2E)

Raman 4 (2A1 + 2E)
Polarized 2 (2A1)
Coincidences 4 (2A1 + 2E)
Silent modes 0

(b) FeCl63–

Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3Fh 6Fd

Ni 7 1 1 3 3 1 1 1 5 3
Pi 3 0 -1 1 -1 -3 -1 0 1 1
'3n 21 0 -1 3 -3 -3 -1 0 5 3

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 '3n = A1g + Eg + T1g + T2g + 3T1u + T2u
'trans = T1u 'rot = T1g
'3n-6 = A1g + Eg + T2g + 2T1u + T2u = 6 frequencies

Infrared 2 (2T1u)
Raman 3 (A1g + Eg + T2g)
Polarized 1 (A1g)
Coincidences 0
Silent modes 1 (T2u)

(c) H2CO

C2v E C2 Fv(xz) Fv(yz)

Ni 4 2 2 4
Pi 3 -1 1 1
'3n 12 -2 2 4

'3n = 4A1 + A2 + 3B1 + 4B2

'trans = A1 + B1 + B2 'rot = A2 + B1 + B2
'3n-6 = 3A1 + B1 + 2B2 = 6 frequencies

Infrared 6 (3A1 + B1 + 2B2)

Raman 6 (3A1 + B1 + 2B2)
Polarized 3 (3A1)
Coincidences 6 (3A1 + B1 + 2B2)
Silent modes 0

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(d) PF5

D3h E 2C3 3C2 Fh 2S3 3Fv

Ni 6 3 2 4 1 4
Pi 3 0 -1 1 -2 1
'3n 18 0 -2 4 -2 4

'3n = 2A1' + A2' + 4E' + 3A2" + 2E"

'trans = E' + A2" 'rot = A2' + E"
'3n-6 = 2A1' + 3E' + 2A2" + E" = 8 frequencies

Infrared 5 (3E' + 2A2")

Raman 6 (2A1' + 3E' + E")
Polarized 2 (2A1')
Coincidences 3 (3E')
Silent modes 0

(e) C2H6 (staggered configuration)

D3d E 2C3 3C2 i 2S6 3Fd

Ni 8 2 0 0 0 4
Pi 3 0 -1 -3 0 1
'3n 24 0 0 0 0 4

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 '3n = 3A1g + A2g + 4Eg + A1u + 3A2u + 4Eu
'trans = A2u + Eu 'rot = A2g + Eg
'3n-6 = 3A1g + 3Eg + A1u + 2A2u + 3Eu = 12 frequencies

Infrared 5 (2A2u + 3Eu)

Raman 6 (3A1g + 3Eg)
Polarized 3 (3A1g)
Coincidences 0
Silent modes 1 (A1u)

(f) H2O2

C2 E C2
Ni 4 0
Pi 3 -1
'3n 12 0

'3n = 6A + 6B
'trans = A + 2B 'rot = A + 2B
'3n-6 = 4A + 2B = 6 frequencies

Infrared 6 (4A + 2B)

Raman 6 (4A + 2B)
Polarized 4 (4A)
Coincidences 6 (4A + 2B)
Silent modes 0

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6.2 (a) SeF5–

C4v E 2C4 C2 2Fv 2Fd

Ni 6 2 2 4 2
Pi 3 1 -1 1 1
'3n 18 2 -2 4 2

'3n = 4A1 + A2 + 2B1 + B2 + 5E

'trans = A1 + E 'rot = A2 + E
'3n-6 = 3A1 + 2B1 + B2 + 3E = 9 frequencies

Infrared 6 (3A1 + 3E)

Raman 9 (3A1 + 2B1 + B2 + 3E)
Polarized 3 (3A1)
Coincidences 6 (3A1 + 3E)
Silent modes 0

(b) AsF4–

C2v E C2 Fv(xz) Fv(yz)

Ni 5 1 3 3
Pi 3 -1 1 1
'3n 15 -1 3 3

'3n = 5A1 + 2A2 + 4B1 + 4B2

'trans = A1 + B1 + B2 'rot = A2 + B1 + B2
'3n-6 = 4A1 + A2 + 2B1 + 2B2 = 9 frequencies

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 Infrared 8 (4A1 + 2B1 + 2B2)
Raman 9 (4A1 + A2 + 2B1 + 2B2)
Polarized 4 (4A1)
Coincidences 8 (4A1 + 2B1 + 2B2)
Silent modes 0

(c) BeF3–

D3h E 2C3 3C2 Fh 2S3 3Fv

Ni 4 1 2 4 1 2
Pi 3 0 -1 1 -2 1
'3n 12 0 -2 4 -2 2

'3n = A1' + A2' + 3E' + 2A2" + E"

'trans = E' + A2" 'rot = A2' + E"
'3n-6 = A1' + 2E' + A2" = 4 frequencies

Infrared 3 (2E' + A2")

Raman 3 (A1' + 2E')
Polarized 1 (A1')
Coincidences 2 (2E')
Silent modes 0

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(d) OSF4

C2v E C2 Fv F v’
Ni 6 2 4 4
Pi 3 -1 1 1
'3n 18 -2 4 4

'3n = 6A1 + 2A2 + 5B1 + 5B2

'trans = A1 + B1 + B2 'rot = A2 + B1 + B2
'3n-6 = 5A1 + A2 + 3B1 + 3B2 = 12 frequencies

Infrared 11 (5A1 + 3B1 + 3B2)

Raman 12 (5A1 + A2 + 3B1 + 3B2)
Polarized 5 (5A1)
Coincidences 11 (5A1 + 3B1 + 3B2)
Silent modes 0

(e) trans-FNNF

C2h E C2 i Fh
Ni 4 0 0 4
Pi 3 -1 -3 1
'3n 12 0 0 4

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 '3n = 4Ag + 2Bg + 2Au + 4Bu
'trans = Au + 2Bu 'rot = Ag + 2Bg
'3n-6 = 3Ag + Au + 2Bu = 6 frequencies

Infrared 3 (Au + 2Bu)

Raman 3 (3Ag)
Polarized 3 (3Ag)
Coincidences 0
Silent modes 0

(f) cis-FNNF

C2v E C2 Fv(xz) Fv(yz)

Ni 4 0 0 4
Pi 3 -1 1 1
'3n 12 0 0 4

'3n = 4A1 + 2A2 + 2B1 + 4B2

'trans = A1 + B1 + B2 'rot = A2 + B1 + B2
'3n-6 = 3A1 + A2 + 2B2 = 6 frequencies

Infrared 5 (3A1 + 2B2)

Raman 6 (3A1 + A2 + 2B2)
Polarized 3 (3A1)
Coincidences 5 (3A1 + 2B2)
Silent modes 0

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(g) S2O32–

C3v E 2C3 3Fv

Ni 5 2 3
Pi 3 0 1
'3n 15 0 3

'3n = 4A1 + A2 + 5E
'trans = A1 + E 'rot = A2 + E
'3n-6 = 3A1 + 3E = 6 frequencies

Infrared 6 (3A1 + 3E)

Raman 6 (3A1 + 3E)
Polarized 3 (3A1)
Coincidences 6 (3A1 + 3E)
Silent modes 0

(h) B2H6

D2h E C2(z) C2(y) C2(x) i F(xy) F(xz) F(yz)

Ni 8 2 2 0 0 2 6 4
Pi 3 -1 -1 -1 -3 1 1 1
'3n 24 -2 -2 0 0 2 6 4

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 '3n = 4Ag + 2B1g + 3B2g + 3B3g + Au + 4B1u + 3B2u + 4B3u
'trans = B1u + B2u + B3u 'rot = B1g + B2g + B3g
'3n-6 = 4Ag + B1g + 2B2g + 2B3g + Au + 3B1u + 2B2u + 3B3u

Infrared 8 (3B1u + 2B2u + 3B3u)

Raman 9 (4Ag + B1g + 2B2g + 2B3g)
Polarized 4 (4Ag)
Coincidences 0
Silent modes 1 (Au)

6.3 C3O2 as C2h

C2h E C2 i Fh
Ni 5 1 1 5
Pi 3 -1 -3 1
'3n 15 -1 -3 5

'3n = 4Ag + 2Bg + 3Au + 6Bu

'trans = Au + 2Bu 'rot = Ag + 2Bg
'3n-6 = 3Ag + 2Au + 4Bu

Comparing these results with those developed in the text (pp. 190-191):

C2h D4h
Infrared 6 (2Au + 4Bu) 4 (2Gu+ + 2Au)
Raman 3 (3Ag) 3 (2Gg+ + Ag)
Polarized 3 (3Ag) 2 (2Gg+)
Coincidences 0 0
Silent modes 0 0

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6.4 In the correlation diagrams shown below, only the species of Td and D4h associated with
normal modes are shown on the left. The frequency numbering of the undistorted structure
has been retained for the distorted structure, with subscripts (a, b, c) for formerly degenerate
modes, to show the fate of individual modes on descent in symmetry.

(a) Distorted tetrahedron (XY4E) - C2v

Td C2v
<1 A1 A1 <1, <2a, <3a, <4a i.r., Raman (pol)
<2 E A2 <2b Raman
<3, <4 T2 B1 <3b, <4b i.r., Raman
B2 <3c, <4c i.r., Raman

(b) Slightly squashed tetrahedron - D2d

Td D2d
<1 A1 A1 <1, <2a Raman (pol)
<2 E B1 <2b Raman
<3, <4 T2 B2 <3a, <4a i.r., Raman
E <3bc, <4bc i.r., Raman

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(c) Square pyramid with X at the apex - C4v

D4h C4v
<1 A1g A1 <1, <3 i.r., Raman (pol)
<2 B1g B1 <2, <5 Raman
<4 B2g B2 <4 Raman
<3 A2u E <6 , <7 i.r., Raman
<5 B2u
<6, <7 Eu

Note that the formerly silent mode, <5 (B2u), of the perfect square plane becomes Raman
active as a result of this distortion.

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(d) Planar MX4 with two long trans positions - D2h (C2' of D4h retained)

D4h D2h
<1 A1g
A1g <1 , <2 Raman (pol)
<2 B1g

<4 B2g B1g <4 Raman

<3 A2u
B1u <3 , <5 i.r.
<5 B2u
B2u <6a, <7a i.r.
<6, <7 Eu
B3u <6b, <7b i.r.

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6.5 Direct correlations from structure I to II to III can be made by using the correlation tables in
Appendix B. A correlation from III to IV cannot be made in this way. Although C2v is a
subgroup of C4v, structure IV is not obtained by retaining pre-existing elements of structure
III. Most significantly, the C2 axis of IV does not exist in III, but rather is newly created.
However, it is possible to make a correlation from II (D4h) to IV (C2v), using the correlation
in Appendix B in which C2" of D4h is retained as the C2 axis of C2v. If a correlation III (C4v)
6 IV (C2v) is attempted, using the correlation tables without realizing the inconsistency of
axis orientations in the two structures, the incorrect results for IV will be 6A1 (R - pol, ir) +
A2 (R) + 4 B1 (R, ir) + 4B2 (R, ir). That the results from the correlation II 6 IV shown below
are correct can be verified by determining the selection rules for IV de novo. By contrast, a
structure whose selection rules could be determined correctly by direct correlation from III
would be trans-MA2B3C. (Structure IV in Fig. 3.1 may be changed to this in the future.)

In the correlation diagrams shown here (I 6 II 6 III, this page, and II 6 IV, next page) only
those symmetry species associated with normal modes are shown. When two or more
frequencies occur with the same symmetry, the number of occurrences is indicated in front
of the Mulliken symbol.

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 I II
Infrared 2 (2T1u) 5 (2A2u + 3Eu)
Raman 3 (A1g + Eg + T2g) 5 (2A1g + B1g + B2g + Eg)
Polarized 1 (A1g) 2 (A1g)
Coincidences 0 0
Silent modes 1 (T2u) 1 (B2u)
III IV
Infrared 8 (4A1 + 4E) 13 (6A1 + 4B1 + 3B2)
Raman 11 (4A1 + 2B1 + B2 + 4E) 15 (6A1 + 2A2 + 4B1 + 3B2)
Polarized 4 (A1) 6 (6A1)
Coincidences 8 (4A1 + 4E) 13 (6A1 + 4B1 + 3B2)
Silent modes 0 0

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6.6 (a) CO2 [O=C=O] Use D2h as a working group.

D2h E C2(z) C2(y) C2(x) i F(xy) F(xz) F(yz)

Ni 3 3 1 1 1 1 3 3
Pi 3 -1 -1 -1 -3 1 1 1
'3n 9 -3 -1 -1 -3 1 3 3

'3n = Ag + B2g + B3g + 2B1u + 2B2u + 2B3u

'trans = B1u + B2u + B3u 'rot = B2g + B3g (not B1g – Rz)
'3n-5 = Ag + B1u + B2u + B3u
Y In D4h, '3n-5 = Gg+ + Gu+ + Au = 3 frequencies

Infrared 2 (Gu+ + Au)

Raman 1 ( G g +)
Polarized 1 ( G g +)
Coincidences 0
Silent modes 0

(b) OCN– [O–C/N]– Use C2v as a working group.

C2v E C2 Fv(xz) Fv(yz)

Ni 3 3 3 3
Pi 3 -1 1 1
'3n 9 -3 3 3

'3n = 3A1 + 3B1 + 3B2

'trans = A1 + B1 + B2 'rot = B1 + B2 (not A2 – Rz)
'3n-5 = 2A1 + B1 + B2
In C4v, '3n-5 = 2E+ + A = 3 frequencies

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 Infrared 3 (2G+ + A)
Raman 3 (2G+ + A)
Polarized 2 (2G+)
Coincidences 3 (2G+ + A)
Silent modes 0

(c) H–C/C–H Use D2h as a working group.

D2h E C2(z) C2(y) C2(x) i F(xy) F(xz) F(yz)

Ni 4 4 0 0 0 0 4 4
Pi 3 -1 -1 -1 -3 1 1 1
'3n 12 -4 0 0 0 0 4 4

'3n = 2Ag + 2B2g + 2B3g + 2B1u + 2B2u + 2B3u

'trans = B1u + B2u + B3u 'rot = B2g + B3g (not B1g – Rz)
'3n-5 = 2Ag + B2g + B3g + B1u + B2u + B3u
Y In D4h, '3n-5 = 2Gg+ + Ag + Gu+ + Au = 5 frequencies

Infrared 2 (Gu+ + Au)

Raman 3 (2Gg+ + Ag)
Polarized 2 (2Gg+)
Coincidences 0
Silent modes 0

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(d) Cl–C/C–H

C2v E C2 Fv(xz) Fv(yz)

Ni 4 4 4 4
Pi 3 -1 1 1
'3n 12 -4 4 4

'3n = 4A1 + 4B1 + 4B2

'trans = A1 + B1 + B2 'rot = B1 + B2 (not A2 – Rz)
'3n-5 = 3A1 + 2B1 + 2B2
In C4v, '3n-5 = 3E+ + 2A = 5 frequencies

Infrared 5 (3G+ +2 A)
Raman 5 (3G+ + 2A)
Polarized 3 (3G+)
Coincidences 5 (3G+ + 2A)
Silent modes 0

(e) H–C/C–C/C–H Use D2h as a working group.

D2h E C2(z) C2(y) C2(x) i F(xy) F(xz) F(yz)

Ni 6 6 0 0 0 0 6 6
Pi 3 -1 -1 -1 -3 1 1 1
'3n 18 -6 0 0 0 0 6 6

'3n = 3Ag + 3B2g + 3B3g + 3B1u + 3B2u + 3B3u

'trans = B1u + B2u + B3u 'rot = B2g + B3g (not B1g – Rz)
'3n-5 = 3Ag + 2B2g + 2B3g + 2B1u + 2B2u + 2B3u
Y In D4h, '3n-5 = 3Gg+ + 2Ag + 2Gu+ + 2Au = 9 frequencies

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 Infrared 4 (2Gu+ + 2Au)
Raman 5 (3Gg+ + 2Ag)
Polarized 3 (3Gg+)
Coincidences 0
Silent modes 0

6.7 (a) '3n-6 = A1' + A2" + 2E' = 4 frequencies Y <1 (A1'), <2 (A2"), <3 (E'), <4 (E')
The systematic assignment of frequency numbers labels nondegenerate modes before
degenerate modes, even though E' is listed before A2" in the current D3h character table.

(b) Association along the C3 axis of the NO3– ion causes its symmetry to descend to C3v. The
changes in spectra can be predicted from the following correlation diagram.

D3h C3v
R. (pol) <1 A1' A1 <1, <2 i.r., R. (pol)
i.r. <2 A2"
i.r., R. <3 , E E <3, <4 i.r., R.
<4

The descent does not lift any degeneracies, but the spectroscopic activities change
significantly. The totally symmetric stretching mode, <1, becomes infrared active. The out-
of-plane deformation mode, <2, becomes a Raman-active polarized mode.

In-plane association causes the NO3– ion's symmetry to descend to C2v. The changes in
spectra can be predicted from the following correlation diagram.

D3h C2v
R. (pol) <1 A1' A1 <1, <3a, <4a i.r., R. (pol)
i.r. <2 A2" B1 <2 i.r., R
i.r., R. <3, <4 E' B2 <3b, <4b i.r., R.

In this case the E' degeneracies of both <3 and <4 are lifted. Thus, both <3 and <4 may split
into two frequencies each, with C2v symmetries A1 and B2, giving a total of six frequencies
active in both the infrared and Raman spectra.

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 The predictions for both modes of association are summarized in the table below.

D3h C3v C2v

Infrared 3 (A2" + 2E') 4 (2A1 + 2E) 6 (3A1 + B1 + 2B2)
Raman 3 (A1' + 2E') 4 (2A1 + 2E) 6 (3A1 + B1 + 2B2)
Polarized 1 (A1') 2 (2A1) 3 (3A1)
Coincidences 2 (2E') 4 (2A1 + 2E) 6 (3A1 + B1 + 2B2)
Silent modes 0 0 0

(c) The data are consistent with the predictions of the C2v model of association.

(d) The 830 cm–1 frequency is <2 (A2"), which is infrared active but Raman inactive for the
"free" ion. The first overtone, 2<2, has A1' symmetry in D3h, which is a Raman active
species. This fundamental becomes Raman active in either the C2v or C3v models of
association. Regardless of the mode of association, the overtone would be Raman active,
since all first overtones of nondegenerate modes are totally symmetric and therefore Raman
active. Failure to observe <2 in the Raman spectrum of 0.3-2.3 M Al(NO3)3 solutions might
seem to suggest that there is no cation-anion or solvent-anion association. However,
association cannot be ruled out, because the fundamental, although Raman allowed by
association, might be very broad and have too weak an intensity to be observed above the
instrumental background.

6.8 (a) True. All even-number direct products of a nondegenerate species give the totally
symmetric representation. Thus, all even-number overtones will belong to the totally
symmetric representation, which is always Raman allowed.

(b) Not always true. Molecules belonging to point groups C1, Cs, Cn, and Cnv have at least
one unit vector transforming as the totally symmetric representation. In these groups, the
even-number overtones will be infrared allowed, as well as Raman allowed. Also, in groups
with degenerate representations, the direct products will be reducible representations, which
may contain an irreducible representation allowing infrared activity.

(c) True. All odd-number direct products of any irreducible representation will be or contain
the original representation. If a vibrational mode is active as a fundamental, it follows that
all its odd-number overtones will be infrared allowed, too.

(d) True. The direct product of any irreducible representation with the totally symmetric
representation is the non-totally symmetric representation. The symmetry-based selection
rules for the non-totally symmetric mode will apply to any combination <s ± <i, because the
symmetry of the combination is the same as <i.

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 (e) True. All first overtones belong to or contain the totally symmetric representation. The
product of the totally symmetric representation with itself is, of course, totally symmetric.
Therefore combinations of the type <s ± 2<i will be Raman allowed.

6.9 (a) The <6 frequency arises from three degenerate T2u modes, which are inactive in both the
infrared and Raman spectra. They are silent modes.

(b) Oh is centrosymmetric, so the rule of mutual exclusion precludes infrared-active modes

from being Raman-active, and vice versa.

(c) 2<4 This should occur at approximately 2 x 262.7 cm-1 = 525.4 cm-1. The observed
frequency (531 ± 3 cm-1) is a little high, but not unreasonably so. The symmetry
of this overtone is T1u x T1u = A1g + Eg + T1g + T2g, making it Raman allowed on the
basis of A1g, Eg, and T2g.

<4 + <6 This should occur at approximately 262.7 cm-1 + 117 cm-1 = 379.7 cm-1, which is
good agreement with the observed 380 ± 3 cm-1. The symmetry of this
combination is T1u x T2u = A2g + Eg + T1g + T2g, making it Raman allowed on the
basis of Eg and T2g.

2<6 If the band at 233 ± 2 cm-1 is assigned as 2<6, then <6 is approximately 117 cm-1.
As shown above, this is consistent with the assignment of the 380 ± 3 cm-1 band to
<4 + <6. The symmetry of the 2<6 overtone is T2u x T2u = A1g + Eg + T1g + T2g,
making it Raman allowed on the basis of A1g, Eg, and T2g. [Note: The symmetry of
T2u x T2u is identical to T1u x T1u, as shown for 2<4 above.] The observed
polarization is consistent with the A1g component.

<1 + <3 This should occur at approximately 741 cm-1 + 739 cm-1 = 1480 cm-1, which is
good agreement with the observed 1479.4 ± 0.5 cm-1. The symmetry of this
combination is A1g x T1u = T1u, making it infrared allowed on the basis of T1u.

<2 + <3 This should occur at approximately 652 cm-1 + 739 cm-1 = 1391 cm-1, which is
good agreement with the observed 1386.9 ± 0.5 cm-1. The symmetry of this
combination is Eg x T1u = T1u + T2u, making it infrared allowed on the basis of T1u.

<2 + <4 This should occur at approximately 652 cm-1 + 263 cm-1 = 915 cm-1, which is good
agreement with the observed 913.1 ± 0.5 cm-1. ± 0.5 cm-1. The symmetry of this
combination is Eg x T1u = T1u + T2u, making it infrared allowed on the basis of T1u.

(d) The combination and overtones observed in the Raman spectrum have gerade symmetry,
and the combinations observed in the infrared spectrum have ungerade symmetry.
Consistent with the rule of mutual exclusion, the Raman-active frequencies cannot be
infrared-active, and vice versa.

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(e) In order to be infrared allowed, a combination would have to be or contain T1u. The
possible combinations with <6, their symmetries, and whether infrared allowed are shown
below.

Combination Symmetries Allowed?

<1 + <6 A1g x T2u = T2u No
<2 + <6 Eg x T2u = T1u + T2u Yes
<3 + <6 T1u x T2u = A2g + Eg + T1g + T2g No
<4 + <6 T1u x T2u = A2g + Eg + T1g + T2g No
<5 + <6 T2g x T2u = A1u + Eu + T1u + T2u Yes

The predicted frequencies for the allowed combinations are:

<2 + <6 . 652 cm-1 + 117 cm-1 = 769 cm-1

<5 + <6 . 317 cm-1 + 117 cm-1 = 434 cm-1

Although allowed, these combinations apparently have too weak intensities to be observed.

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