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Abstract
Raman and FTIR, spectra of nitrobenzene, nb, and its isotopomers, nb-15N, nb-13C6 and nb-d5 ; were obtained and the
fundamental vibrational modes assigned with the aid of a B3LYP/6-311 þ G** calculation, without the need for scaling of the
force constants. The changes in vibrational coupling between the nitro and benzene groups upon certain isotopic substitutions
are well modelled by the calculation, which is able to reproduce the isotopic shifts in frequencies for the nitro vibrations, as well
as changes in IR intensities.
q 2003 Elsevier B.V. All rights reserved.
Keywords: Density functional theory; Isotopomers; Vibrational analysis
of force constants for molecules such as nitrobenzene excitation. FTIR spectra were obtained using a
and 2-nitrophenol was needed as it was thought that a Nicolet Impact 400D.
purely computational approach to the force field or Geometry optimisation and frequency analysis of
frequencies for such molecules was not possible. nitrobenzene was performed using GAUSSIAN 98 [18]
Systematic calculation errors were compensated for with the B3LYP hybrid density functional [19,20]
and good agreement with the observed experimental using the 6-31G* [21 –23] and 6-311 þ G** [24,25]
frequencies was achieved by using a few empirical basis sets.
scale factors for the calculated force constants
[15,16].
The present authors reported a recent successful 3. Results and discussion
DFT analysis of the structure and vibrations of 2,4,6-
trinitrotoluene, TNT, using the hybrid density func- Computed bond lengths and angles for nitroben-
tional B3LYP and the 6-311 þ G** basis set [17], zene together with the electron diffraction and
without the need to scale the force constants or microwave data (Fig. 1) are shown in Table 1.
frequencies. The good fit between the theoretical and Previous MP2 calculations showed the C –C bonds as
experimental frequencies for TNT was only achieved getting longer the farther away from the NO2 group
by use of the triple zeta, 6-311 þ G** basis set; A attachment point, in contrast to the HF calculation
B3LYP calculation of TNT with the double zeta, 6- [15]. The present B3LYP calculations is in agreement
31G* basis set gave poor results. Following this, the with the HF calculation in that only the farthest away
authors decided to re-examine the vibrational spectra CC bond length is notably longer, the other two being
of nitrobenzene to test if a similar DFT analysis could near equal. There is a large difference in the CN and
successfully model the vibrational spectra of nitro- NO bond lengths modelled by the B3LYP calculations
benzene and account for the isotopic shifts without the compared to previous HF and MP2 calculations. The
need to rescale the force constants. improvement in the MP2 NO2 bond lengths over the
We present FTIR and Raman data for liquid HF values is in increasing the CN bond length,
nitrobenzene, nb, nb-d5 ; nb-15N, and nb-13C6 and however, it overestimates the NO bond length [15].
assign the spectra on the basis of a B3LYP/6- The B3LYP calculations increase further the CN bond
311 þ G** calculation. The changes in the length, but decreases the NO bond length. The effect
vibrational mode coupling between the nitro group of the 6-311 þ G** basis set on the B3LYP
and the benzene ring for the various isotopomers are functional, compared to the B3LYP/6-31G* structure
well modelled by the B3LYP/6-311 þ G** calcu-
lation and previous assignments of the vibrational
spectra are revised. The present analysis represents a
reappraisal of the analysis of Shlyapochnikov et al.
[15], presenting new vibrational data for nb-13C6 and
new insights into the coupling of the nitro and
benzene modes.
2. Methods
Table 1
Computed B3LYP/6-311 þ G** bond lengths and angles for nitrobenzene
HF 6-31G*a MP2 6-31G*a MP2 6-31G**a B3LYP 6-31G* B3LYP 6-311 þ G** Microwavea
Table 2
Vibrational assignment of nitrobenzene, nb and nb-15N, nb-13C6 and nb-d5
Table 2 (continued)
Table 2 (continued)
Table 3
List of observed and calculated isotopic frequency shifts for the C– NO2 moiety for nitrobenzene. Values in parenthesis calculated by
Shlyapochinkov et al [15].
No. Vibration nb-13C6a nb-15Na nb-d5a Nb-16O,18O [15] Nb-18O2 [15] Para-d-nb [15]
Obs. Calc. Obs. Calc Obs. Calc. Obs. Calc. Obs. Calc. Obs. Calc.
*1 nas NO2 210 221.0 228 230.4 26 29.4 213 210.8 221 223.7 24 23.5
(227.9) (213.7) (25.1) (220.1) (26.0)
*2 23 21.1 223 222.9 þ14, 26 þ 5.2 214 216.9 227 235.2 21 0.0
(225.7) (þ7.7), 22.7 (28.3), 220.9 (229.2) (20.1)
*3 n CN 227 229.3 21 20.8 231 233.3 24 22.3 24.6 0 20.1
(20.2) (240.3) (22.3) (28.8) (20.1)
*4 d ONO 26 25.8 26 27.1 27 27.1 212 27.2 226 229.1 0 20.7
(26.0) (23.1) (27.3) (28.4) (20.6)
*5 v NO2 29 28.5 26 24.6 273 265.4 0 20.6 22 21.3 230 236.4
(25.5) (þ15.5) (20.4) (21.6) (233.9)
*6 23 22.0 28 212.5 290 290.7 0 22.1 22 24.3 214 25.1
(210.8) (219.7) (21.0) (23.7) (214.2)
*7 t NO2 26 25.5 22 22.5 219 213.8 212 28.2 224 216.5 22 21.2
(22.3) (213.4) (24.3) (216.2) (21.3)
*8 x NO2 20.6 0.0 21.7 20.8 21.5 0.0
(0.0) (21.2) (20.5) (22.0) (0.0)
Notation: n; d; v; t; and x-stretching, bending, wagging, rocking and tortional vibrations, respectively; a, as-symmetric and antisymmetric.
a
Observed values from our own data shown on Fig. 2, Table 2.
NO2 mode mixes with benzene mode 11, yielding the non-C – H stretching mod, (n6; Fig. 3) is predicted to
two *5 and *6 modes. This NO2 mode also mixes with have the second highest IR intensity, Fig. 4. The
benzene mode 11 in nb-d5 giving the largest isotopic benzene 8b mode of nitrobenzene is involved in Fermi
shift in Table 3, due to the large contribution from C – resonance with the combination mode 12 þ 6b,
H/D out of plane bending in these modes. Shlyapo- (1004 þ 611 cm21), resulting in two IR bands at
chinkov et al. calculate þ 19.7 and 2 13.4 cm21 shifts 1620 and 1606 cm21. Identical Fermi resonance is
for nb-d5 modes *5 and *6, respectively, which observed for nb-15N and also for nb-13C6, were two
the present analysis suggests are incorrectly assigned strong bands, at 1568 and 1553 cm21, are observed.
[15]. The present calculation predicts that of all the The increased contribution of the nb-13C6 asymmetric
isotopomers of nitrobenzene, except for nb-d5, the *6 nitro stretch to the highest non C – H stretching mode,
mode has the highest contribution from the NO2 of-of- modelled by the calculation, is shown by the large
plane deformation mode. It appears that the *5 band of increase in IR absorption for these Fermi resonance
nb-d5 was mistaken for the nitrobenzene *6 band by bands, Fig. 4.
Shlyapochinkov et al. [15]. The 1620 and 1606 cm21 IR bands were correctly
There is very good agreement between our identified as a Fermi resonance pair by Kuewae and
calculated isotopic shifts and those observed exper- Machida, though the benzene mode combination band
imentally, Tables 2 and 3, giving extra confidence in was wrongly identified as 1 þ 6b [13]. These bands,
the modelled vibrations. Table 4 shows our calculated however, were incorrectly assigned to fundamentals
frequencies for all of the isotopomers of nitrobenzene by Shlyapochinkov et al. [15]. There are many
studied to date, including nb-18O16O, nb-18O2 and nb- combinations and overtones present in the Raman
p-d1. and IR spectra of the nitrobenzene above 1650 cm21,
The asymmetric nitro vibration *1, is calculated which we have not assigned. Combinations and
to couple to the benzene mode 8b, (n6 and n8 for nb overtones below 1650 cm21 have been assigned to
and nb-13C6, Fig. 3). The degree of this mixing fully account for all bands in the fundamental region
dramatically changes in nb-13C6, where the highest of the spectra, Table 2.
420 J. Clarkson, W. Ewen Smith / Journal of Molecular Structure 655 (2003) 413–422
Table 4
B3LYP/6-311 þ G** frequencies for nitrobenzene isotopomers
13
C6H5NO2 C6H5NO2 C6H15
5 NO2 C6H5N18O2 C6H5N16O18O d5-C6H5NO2 p-d1-C6H4NO2
The symmetric nitro vibration, *2, does not shift 1341 cm21, which are both assigned to the symmetric
much in energy for nb-13C6, revealing the lack of nitro stretch, *2. This nitro mode mixes with the
involvement of the benzene ring in this mode. benzene mode 19a, giving two modes, (nb-d5 n9 and
The principle CN mode *3, does however show a n11; Fig. 3), with differing contributions from the
large shift in frequency for nb-13C6, which is nitro group; they also differ in the phases of the
tentatively assigned to be involved in Fermi resonance benzene and nitro group contributions. These two
with the combination mode n34 þ n24; to give two intense nitro bands are amongst a group of four bands
bands at 1082 and 1073 cm21. found between 1390 and 1310 cm21, Fig. 5. The
The most notable change to the vibrational spectra calculation predicts the negatively shifted isotopic
of nb-d5 are the two intense bands at 1360 and band to have the greatest contribution from the nitro
J. Clarkson, W. Ewen Smith / Journal of Molecular Structure 655 (2003) 413–422 421
mixing with benzene mode 14, Fig. 3. This gives rise [7] S. Daehne, H. Stanko, Spectrochim. Acta 18 (1962) 561.
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