Spectrochimica Acta Part A 92 (2012) 137147

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Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
j our nal homepage: www. el sevi er . com/ l ocat e/ saa
Vibrational spectroscopic studies, molecular orbital calculations and chemical
reactivity of 6-nitro-m-toluic acid
V. Balachandran
a,
, T. Karthick
b
, S. Perumal
c
, A. Nataraj
d
a
Department of Physics, A.A Government Arts College, Musiri, Tiruchirappalli 621201, India
b
Department of Physics, Vivekanandha College for Women, Tiruchengode 637205, India
c
Department of Physics, S.T. Hindu College, Nagercoil 629002, India
d
Department of Physics, Thanthai Hans Roever College, Perambalur 621212, India
a r t i c l e i n f o
Article history:
Received 18 September 2011
Received in revised form26 January 2012
Accepted 14 February 2012
Keywords:
6-Nitro-m-toluic acid
Vibrational spectra
Dimer
NBO
Frontier molecular orbitals
MEP surface
a b s t r a c t
The potential energy surface scan for the selected dihedral angle of 6-nitro-m-toluic acid (NTA) has been
performed to identify stable conformer. The optimized structure parameters and vibrational wavenum-
bers of stable conformer have been predicted by density functional B3LYP method with 6-311++G(d,p)
basis set. The formation of dimer species through carboxylic acid group of the title molecule has also been
discussed. The theoretical dimer geometries have been compared with that of monomer and the varia-
tions of bond lengths and bond angles upon dimerization were also discussed. Natural bond orbital (NBO)
analysis has been performed on both monomer and dimer geometries. The signicant changes in occu-
pancies and the energies of bonding and anti-bonding orbitals upon dimerization have been explained in
detail. The predicted frontier molecular orbital energies at B3LYP/6-311++G(d,p) method set show that
charge transfer occurs within the molecule. The nucleophilic and electrophilic sites obtained from the
molecular electrostatic potential (MEP) surface were compared with their derived tting point charges.
The vibrational wavenumbers of NTA affected profusely by the nitro group substitution in comparison
to the toluic acid have been interpreted in this work.
Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.
1. Introduction
m-Toluic acid and its derivatives are widely used in the
manufacture of polymer stabilizers, pesticides, light sensitive com-
pounds, animal feed supplements and other pharmaceuticals,
pigments and dyestuff [1]. In addition, m-toluic acid is widely
used as a raw material for producing most chemically impor-
tant compounds such as m-toluoyl chloride, m-tolunitrile and
N,N-diethyl-m-toluamide. In industry, they are being used as a
broad-spectrum insect repellent, low fogging thermal stabilizers
and lm formers. In particular, the 6-nitro-m-toluic acid (also
regarded as 5-methyl-2-nitro benzoic acid) is being used as inter-
mediatefunctional dyes andinthesynthesis of organic compounds.
Derivatives of benzoic acid have been the subject of vibrational
investigation for many reasons. A derivative of benzoic acid is
an essential component of the Vitamin B complex. Benzoic acid
occurs widely in plants and animal tissues along with Vitamin
B complex and is used in miticides, contrast media in urology,

Corresponding author. Tel.: +91 431 2432454; fax: +91 432 6262630.
E-mail address: brsbala@rediffmail.com(V. Balachandran).
cholocystrographic examinations and in the manufacture of phar-
maceuticals [2].
Because of its wide applications, vibrational spectra of benzoic
acidandthe substitutedbenzoic acids have beenstudiedby various
spectroscopists [214]. IR and Raman spectra of benzoic acid and
its deuterated benzoic acids at lowtemperature have been investi-
gated by Furic and Durig [3]. The detailed vibrational assignments
of ortho-substituted benzoic acid derivatives have been reported
by Sanchez et al. [4]. They have proposed the inuence of different
substituents on the frequency of ring vibrational modes of ben-
zoic acid. Verma et al. recorded the infrared absorption spectrum
of m-urobenzoic acid in the region 2504000cm
1
[5]. The com-
bined theoretical and experimental FT-IR and FT-Raman spectral
studies of intumescent agent known as 5-amino-2-nitro benzoic
acid have been performed by Ramalingamet al. [2]. Sundaragane-
san et al. investigated the vibrational features of various amino
and halogenated benzoic acids by FT-IR and FT-Raman spectra
[610]. Ahamed et al. [11] recorded the laser Raman and FT-IR
spectra of 3,5-dinitrobenzoic acid in the region 2504000 and
504000cm
1
, respectively. The infrared and laser Raman spec-
tra of solid 2,3,5- and 3,4,5-triiodobenzoic acid in various solvents
have been reported by Goel and Gupta [12]. The infrared absorp-
tion spectra of 2-chloro-5-nitrobenzoic acid have been studied by
1386-1425/$ see front matter. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2012.02.048
138 V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147
Rastogi et al. [13]. Recently, vibrational spectroscopic studies have
been performed on the solid phase of toluic acid by Babu et al. [14].
In benzoic acid crystals, the dimerization takes place through
the hydrogenbonds across a center of symmetry. Besides monomer
geometry, the dimeric species of benzoic acidderivatives have been
extensively investigated earlier. The infrared spectra of benzoic
acid monomer and normal coordinate analysis of both monomer
and dimer geometries have been reported by Reva and Stepanian
[15]. Quantumproton transfer and the interconversion in benzoic
acid dimer have been reported by Fillaux et al. [16]. Theoreti-
cal model of benzoic acid dimer and symmetric proton stretching
vibrations in the centrosymmetric dimers through the hydrogen
bonds have beenstudiedby Flakus andChelmecki [17]. Boczar et al.
reported the combined experimental and calculated vibrational
wavenumbers of benzoic acid and salicylic acid dimer [18,19].
Experimental FT-Raman, FT-IR and theoretical dimer conformer of
5-bromosalicylic acid [20] and 5-uro, 5-chlorosalicylic acid [21]
have been studied by Karabacak et al.
Literature survey reveals that to the best of our knowledge
the vibrational studies, molecular orbital (MO) calculations and
the chemical reactivity of 6-nitro-m-toluic acid (NTA) have not
been performed so far. Therefore, an attempt has been made in
the present work to study the detailed experimental (FT-IR and
FT-Raman) and theoretical (DFT) investigation of the vibrational
spectra of NTA. In this study optimized molecular parameters and
MO calculations (such as NBO and HOMOLUMO) for the stable
monomer and dimer conformer of NTA are predicted. The assign-
ments of vibrational wavenumbers of the title molecule are being
reportedalong withthe percentage of potential energy distribution
(PED) results obtained from MOLVIB program (Version 7.0-G77)
written by Sundius [22]. The variations in geometrical parameters
and the electron density of atoms of the molecule upon dimeriza-
tion are also interpreted in this work.
2. Experimental procedure
The crystalline sample of NTA is purchased fromSigma Aldrich
chemical suppliers (India) with the stated purity of 98%. Then,
the compound is used for spectral measurements without fur-
ther purication. In the present study, the Fourier transform
infrared spectrum(FT-IR) of the title compound is recorded in the
wavenumber region 4004000cm
1
on a NEXUS 670 spectropho-
tometer equipped with an MCT detector in a KBr pellet technique.
The FT-Raman spectrum is recorded in the wavenumber region
1003500cm
1
ona NEXUS 670spectrophotometer equippedwith
Raman module accessory operating at 1.5W power with Nd:YAG
laser of wavelength 1064nm is used as an excitation source. The
spectral measurements were carried out at Sree Chitra Tirunal
Institute for Medical Sciences and Technology, Poojappura, Thiru-
vanathapuram, Kerala, India.
3. Computational details
The potential energy surface (PES) scan for the selected dihe-
dral angle (C
1
C
7
O
9
H
10
) of the title molecule is performed at
B3LYP/6-311++G(d,p) level of density functional theory (DFT) in
Gaussian 03W software package [23]. Then, the optimized geo-
metrical parameters of stable monomer and dimer conformer are
computed at B3LYP/6-311++G(d,p) basis set method. The dimer
geometry of NTA molecule is formed by an anharmonic cou-
pling model as described by Marechal and Witkowski, and Wojcik
[24,25]. An anharmonic coupling is the coupling between the high
frequency O Hstretching and lowfrequency intermolecular O O
hydrogen bond stretching vibrations. It is an important mechanism
for shaping the ne structure of stretching bands in the hydrogen-
bonded systems.
The theoretical vibrational wavenumbers of the title molecule
are calculated by assuming C1 point group symmetry. The com-
puted vibrational wavenumbers at B3LYP/6-311++G(d,p) show
that, there are some disagreements with the experimental
wavenumbers. These discrepancies are mainly due to the neglect
of anharmonicity effect at the beginning of harmonic wavenumber
calculation and basis set deciencies. In the present work, theoret-
ical wavenumbers are scaled down by six different scale factors.
The MO calculations such as NBO and HOMOLUMO calculations
are performed on the stable monomer and dimer geometry of NTA.
The occupancy numbers, energies and second order perturbation
energies of interacting Lewis base and Lewis acid sites are reported
with the help of NBO 3.1 programas stored in Gaussian 03Wpack-
age. Moreover, the molecular electrostatic potential (MEP) surface
map is plotted over the optimized electronic structure of NTAusing
the same level of DFT theory. In this work, the electrophilic and
nucleophilic sites obtained in the MEP surface are being compared
with derived tting point charges to the electric potential.
3.1. Prediction of Raman intensities
Initially, the Raman scaterring activities (S
i
) obtained from the
Gaussian 03Wprogramare adjusted during the scaling procedure
with MOLVIB. Then, they are subsequently converted to relative
Ramanintensities (I
i
) using the following relationshipderivedfrom
the intensity theory of Raman scattering [26,27].
l
i
=
j (v
0
v
i
)
4
S
i
v
i
[1 exp(hcv
i
]k
b
1)]
where v
0
is the exciting frequency (1064nm=9398cm
1
) of laser
light source used while recording Raman Spectra, v
i
the vibrational
wavenumber of the ith normal mode. h, c and k
b
fundamental con-
stants, and f is a suitably chosen common normalization factor for
all peak intensities of the Raman spectrumof the title molecule.
4. Result and discussion
The present compound under investigation has become great
interest because it contains three different substituents namely
methyl group ( CH
3
), carboxyl group ( COOH), and nitro group
( NO
2
) connected with the benzene ring. For getting stable con-
former of NTA, the relaxed scan is applied to the most interacting
dihedral angle (C
1
C
7
O
9
H
10
) of the carboxyl group. In relaxed
scan, the variables corresponding to the selected dihedral angle of
NTA are varied in steps of 10

between 0

and 350

. While per-
forming the scan in Gaussian 03W, the programis searching global
local minimumpoint for each 10

. The Eigen values obtained from

the scan output reveals that, the structure positioning the dihe-
dral angle (C
1
C
7
O
9
H
10
) at 180

possesses minimum energy

among others. The optimized geometry of NTA is shown in Fig. 1
and potential energy curve between the dihedral angles and their
corresponding energies is given in Fig. 2.
4.1. Geometrical parameters of stable monomer and dimer
The predicted geometrical parameters such as bond lengths and
bondangles of NTAcalculatedat B3LYPmethodwith6-311++G(d,p)
are presented in Table 1 in accordance with the atom numbering
scheme as given in Fig. 1. Since the experimental X-ray diffrac-
tion data of NTA molecule is unavailable, the experimental data
of similar kind of molecule is presented in Table 1 for comparative
purpose [28]. Whencomparing experimental values, the computed
bond lengths and bond angles at B3LYP/6-311++G(d,p) method are
V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147 139
Table 1
Optimized geometrical parameters of stable monomer and dimer of 6-nitro-m-toluic acid computed at B3LYP/6-311++G(d,p) basis sets.
Bond lengths
a
Theoretical bond lengths Experimental data
b
Bond angles
a
Theoretical bond angles Experimetal data
b
Monomer Dimer Monomer Dimer
C
1
C
2
1.3995 1.3995 1.3878 C
2
C
1
C
6
118.06 118.04 119.96
C
2
C
3
1.3874 1.3874 1.3850 C
2
C
1
C7 124.90 124.93 120.70
C
3
C
4
1.3912 1.3912 1.3860 C
6
C
1
C7 116.98 116.98 119.34
C
4
C5 1.3973 1.3973 1.3910 C
1
C
2
C
3
121.33 121.36 119.35
C5 C
6
1.4001 1.4001 1.3890 C
1
C
2
N
11
121.22 121.18
C
1
C
6
1.3931 1.3931 1.3940 C
3
C
2
N
11
117.30 117.31
C
1
C7 1.5001 1.5003 1.4780 C
2
C
3
C
4
119.40 119.39 120.18
C
2
N
11
1.4763 1.4763 C
2
C
3
H
14
119.21 119.21 119.9
C
3
H
14
1.0819 1.0819 0.9500 C
4
C
3
H
14
121.38 121.39 119.9
C
4
H
15
1.0842 1.0842 0.9500 C
3
C
4
C5 121.02 121.01 121.38
C5 C
16
1.5073 1.5073 1.5060 C
3
C
4
H
15
119.20 119.20 119.30
C
6
H
20
1.0841 1.0841 0.9500 C5 C
4
H
15
119.77 119.78 119.30
C7 O
8
1.2041 1.2195 1.2562 C
4
C5 C
6
118.22 118.24 117.90
C7 O
9
1.3482 1.3192 1.2909 C
4
C5 C
16
121.40 121.40 121.23
O
9
H
10
0.9695 0.9969 0.9840 C
6
C5 C
16
120.38 120.36 120.86
N
11
O
12
1.2233 1.2231 C
1
C
6
C5 121.94 121.94 121.21
N
11
O
13
1.2238 1.2241 C
1
C
6
H
20
118.02 118.04 119.40
C
16
H
17
1.0947 1.0947 0.980 C5 C
6
H
20
120.04 120.02 119.40
C
16
H
18
1.0929 1.0923 0.980 C
1
C7 O
8
123.94 123.96 120.38
C
16
H
19
1.0911 1.0911 0.980 C
1
C7 O
9
112.12 112.07 116.63
O
9
O
12
2.8191 2.8201 O
8
C7 O
9
123.78 123.78 122.99
O
8
H
24
1.500 0.9980 C7 O
9
H
10
107.66 107.63 112.50
O
9
H
10
O
22
1.1318 0.9840 C
2
N
11
O
12
117.29 117.30
C
2
N
11
O
13
117.43 117.43
O
12
N
11
O
13
125.24 125.23
C5 C
16
H
17
111.43 111.40 109.50
C5 C
16
H
18
111.20 110.15 109.50
C5 C
16
H
19
110.68 110.76 109.50
H
17
C
16
H
18
108.24 108.25 109.50
H
17
C
16
H
19
107.85 107.80 109.50
H
18
C
16
H
19
107.27 107.30 109.50
C7 O
9
O
12
77.11 76.83
H
10
O
9
O
12
114.09 102.18
N
11
O
12
O
9
84.94 85.20
a
For atomnumbering scheme, see Fig. 1.
b
Ref. [28]
slightly larger, because the theoretical calculations are performed
upon isolated molecule in the gaseous state and the experimental
results are performed on the solid phase of the molecule [29].
In the case of free (with no substituents) benzene, the bond
lengths between the carbon atoms held together in the hexagonal
chain are almost equal. If so, there must be a change in bond length
occurs according to the nature of substituents. In the title molecule,
the calculated C C bond lengths of the benzene ring varies from
1.3874 to 1.4001

A whereas outside the ring, C C bonds lengths
exceeds by an amount 0.10.12

A. Similarly, aromatic C H bond
lengths are of the order of 1.08

A and that of methyl 1.09

A. It is
Fig. 1. Optimized molecular structure of 6-nitro-m-toluic acid.
worthmentioningthat, the bondlengths of NTAmonomer reported
in Table 1 are matched well with that of the optimized electronic
structure of NTA dimer except few. The variations of bond lengths
upon dimerization may due to the delocalization of electron den-
sityfromelectrondonor toacceptor atom. For example, the O
9
H
10
bond length of the monomer is reported as 0.9695

A and that of
dimer 0.9969

A. Thus upondimerization, the O
9
H
10
bondlengthis
increased by 0.0274

A may cause the formation of hydrogen bond-
ing interactions with the neigbouring molecule. Likewise, the bond
length C
7
O
8
is increased by 0.0154

A upon dimerization.
The C Hbond length such as C
3
H
14
, C
4
H
15
, C
6
H
20
, C
6
H
17
,
C
7
H
18
andC
6
H
20
calculatedat B3LYP/6-311++G(d,p) aretoolong
incomparion with the experimental values. It is well known that
DFT method predict bond lengths that ate systematically too long,
especially in C H bond lengths [30].This may due to that, the low
Fig. 2. Potential energy surface scan for the selected (C
1
C7O
9
H
10
) dihedral
angle of 6-nitro-m-toluic acid.
140 V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147
Fig. 3. Dimer conformer of 6-nitro-m-toluic acid.
scattering factor of hydrogen atoms involved in the X-ray diffrac-
tion experiment produces large deviation fromthe theoretical C H
bond lengths. The bond lengths of the strong intermolecular inter-
actions viz. O
9
H
10
O
22
and O
23
H
24
O
8
of dimer conformer
are calculated as 1.1318

A and 1.5000

A, respectively. The weak
intramolecular hydrogen bond between C
7
O
9
and N
11
O
12
is cal-
culated as 2.8191

A for the monomer and 2.8201

A for the dimer
conformer of NTA.
For considering free benzene, the hexagonal angles such as
C C C and C C H bond angles corresponding to the stable
monomer and dimer conformer of NTA are slighty deviated by
1

. This is because of the fact that, the C C C and C C H bond

angles of the benzene ring are substituent sensitive. Therefore a
single substituent can alters the entire geometry of the molecule.
Moreover, the bondangles between the inter- and intramolecu-
lar fragments (C
7
O
9
O
12
, H
10
O
9
O
12
, and N
11
O
12
O
9
) are
greatly affected by the dimerization process and are also depicted
in Table 1.
4.2. NBO analysis
In hydrogen bonded systems, the stability of the molecule
may cause several factors; hyperconjugative interactions, inter-,
intramolecular hydrogen bonding, intermolecular charge trans-
fer (ICT), electron density transfer (EDT) and cooperative effect
due to the delocalization of electron density from the lled
lone pairs of Lewis base n(y) into the unlled antibonding of
Lewis acid o*(x H) or *(x H). It is found from the literature
that, natural bond orbital (NBO) analysis is an effective tool for
determining the above mentioned factors [31]. In the present
work, NBO analysis has been performed on the monomer and
dimer with the aid of NBO 3.1 program as implemented in the
Gaussian 03W package. The dimer structure shown in Fig. 3 con-
sists of a couple of inter- and intramolecular hydrogen bonding
interactions. In the case of NTA, the intermolecular interactions
are formed by the orbital overlap between n(O) and o*(O H)
{i.e. n(O
8
) o*(O
23
H
24
), n(O
22
) o*(O
9
H
10
)}. Similarly, the
intramolecular hydrogen bonding is present in between the nitro
group and carboxylic group of NTA dimer. Since intramolecular
interactions are very week, the ICT and EDT between n(O
12
) and
o*(O
9
H
10
) or n(O
34
) and o*(O
21
H
22
) are not appreciable.
Furthermore, the NBO analysis of NTA monomer and dimer
clearly gives the evidence for the formation of strong intermolecu-
lar andveryweekintramolecular interactions betweenoxygenlone
electron pairs and o*(O H) antibonding orbitals. In Table 2, the
occupation numbers along with the energies of interacting NBOs
are being presented. The magnitude of charges transferred from
the lone pairs of n(O
8
) into the antibonding orbital o*(O
9
H
10
) is
signicantly increased by 0.0397e and 0.0481e, respectively, upon
dimerization. The variations in the magnitude of charges provided
an unambiguous evidence for the weakening of C
7
O
8
, O
9
H
10
bonds and their elongation. As it can be seen fromTable 2 that, the
magnitude of charge transferred between n(O
13
) and o*(O
9
H
10
)
is not signicant. Therefore a similar conclusion can be obtained
while considering the energy of the corresponding orbitals.
The stabilization energy E(2) associated with the hyper-
conjugative interactions viz. n
1
(O
8
) o*(O
23
H
24
) and
n
1
(O
21
) o*(O
9
H
10
) are obtained 21.45 and 18.24kcal mol
1
,
respectively, as shown in Table 3. It is worth mentioning that,
the differences in stabilization energies reported in Table 3 are
reasonable. In view of the fact that, the accumulation of electron
density in the antibonding orbital o*(O H) is not only transferred
fromthe lone electron pair n(O) but also fromthe entire molecule.
Unusually, rehybridization plays a negative effect in O
9
H
10
bond. It is observedinTable4that, thes-character of O
9
H
10
hybrid
orbitals increases (18.03%) fromsp
3.70
to sp
1.54
that leads to a con-
spicuous strengthening of O
9
H
10
bond and its contraction. This
shows the existence of a mesomeric structure characterized by
the delocalization of electron density from the o*(O
9
H
10
) anti-
bonding orbital to the remaining part of the molecule. This is quite
possible because the energy of o*(O
9
H
10
) antibonding orbital
(0.4561a.u.) is higher than the energy of o*(C
7
O
9
) antibonding
orbital (0.3633a.u.) which supports the likelihood of the delocal-
ization of ED from O H to C O region. This is clearly reected
in the dimer geometry of NTA as the bond C
7
O
9
contracts to
an amount of 0.0290

A with respect to the monomer. The natu-
ral atomic hybrids corresponding to the H-bonded NBO also shows
that the redistribution of natural charges in O Hbond destabilizes
the H-bond. Because both the hyperconjugation and rehybridiza-
tion are in opposite directions, the compression and elongation of
the bond O His a result of the balance of the two effects. However
the hyperconjugative interaction is dominant and overshadows
the rehybridization effect resulting a signicant elongation in O H
bond (0.0274

A) with respect to the monomer.
The ED of the carbonyl group antibonding orbitals o*(C
7
O
8
)
and *(C
7
O
8
) are increased signicantly (0.0303e and 0.0446e,
respectively) upon dimerization. This clearly gives the evidence for
the weakening of C
7
O
8
bond and its elongation (0.0154

A). This
is also evident that, the stabilization energy E(2) reported to the
hyperconjugativeintramolecular interactions n
1
(O
9
) o*(C
7
O
8
),
V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147 141
Table 2
Occupancies and energies of interacting Lewis base and Lewis acid sites of 6-nitro-m-toluic acid.
Parameters Occupancies (e) z
Occ
(e) Enegy (a.u) zE (a.u)
Monomer Dimer Monomer Dimer
n
1
(O
8
) 1.9788 1.9391 0.0397 0.7227 0.6922 0.0305
n
2
(O
8
) 1.8425 1.8602 0.0177 0.2895 0.3141 0.0246
n
1
(O
9
) 1.9762 1.9612 0.015 0.6482 0.5586 0.0896
n
2
(O
9
) 1.8177 1.7438 0.0739 0.3585 0.3088 0.0497
n
1
(O
12
) 1.9809 1.9807 0.0002 0.8218 0.8080 0.0138
n
2
(O
12
) 1.8941 1.8931 0.0010 0.3134 0.2995 0.0139
n
1
(O
13
) 1.9816 1.9816 0.0000 0.8216 0.8089 0.0127
n
2
(O
13
) 1.8981 1.8981 0.0000 0.3118 0.2993 0.0125
n
3
(O
13
) 1.4373 1.4413 0.0040 0.2961 0.2837 0.0124
o* (C
1
C
2
) 0.0302 0.0297 0.0005 0.5259 0.5357 0.0098
o* (C
1
C
6
) 0.0188 0.0194 0.0006 0.5396 0.5501 0.0105
* (C
1
C
6
) 0.3215 0.3200 0.0015 0.0007 0.0100 0.0093
o* (C
1
C7) 0.0704 0.0662 0.0042 0.3734 0.3643 0.0091
o* (C
2
C
3
) 0.0212 0.0209 0.0003 0.5337 0.5446 0.0109
* (C
2
C
3
) 0.3583 0.3545 0.0038 0.0081 0.0027 0.0054
o* (C
2
N
11
) 0.1032 0.1033 0.0001 0.2479 0.2598 0.0119
o* (C7 O
8
) 0.0241 0.0544 0.0303 0.5804 0.5340 0.0464
* (C7 O
8
) 0.2165 0.2611 0.0446 0.0011 0.0632 0.0621
o* (C7 O
9
) 0.0991 0.0818 0.0173 0.3253 0.3633 0.038
o* (O
9
H
10
) 0.0106 0.0587 0.0481 0.3657 0.4561 0.0904
o* (N
11
O
12
) 0.0671 0.0656 0.0015 0.4002 0.4150 0.0148
* (N
11
O
12
) 0.6034 0.5972 0.0062 0.1384 0.1252 0.0132
o* (N
11
O
13
) 0.0617 0.0620 0.0003 0.4085 0.4212 0.0127
Table 3
Second order perturbation theory analysis of Fock Matrix in NBO basis.
Donor (i) Acceptor (j) E(2) kcal mol
1
E(j) E(i) a.u. F(i,j) a.u.
Within unit 1
n
1
(O
8
) o* (C7 O
9
) 3.02 1.06 0.051
n
2
(O
8
) * (C7 O
9
) 25.24 0.68 0.118
n
1
(O
9
) o* (C7 O
8
) 8.49 1.09 0.086
n
2
(O
9
) * (C7 O
8
) 39.49 0.37 0.108
n
1
(O
12
) o* (N
11
O
13
) 2.55 1.23 0.051
n
1
(O
12
) o* (C
2
N
11
) 4.21 1.07 0.061
n
1
(O
13
) o* (N
11
O
12
) 2.54 1.22 0.050
Fromunit 1 to unit 3
n
1
(O
8
) o* (O
23
H
24
) 21.45 1.15 0.140
Within unit 3
n
1
(O
22
) o* (O
9
H
10
) 18.24 1.02 0.087
n
1
(O
22
) o* (C
21
O
23
) 23.30 0.61 0.107
Table 4
Composition of hydrogen bonded NBOs interms of natural atomic hybrids.
Hydrogen bonded NBOs Monomer Dimer z
NBO
sp
n
(O
9
H
10
) sp
3.70
sp
1.54
+s
% of s character 21.26% 39.29% +18.03
% of p character of O
9
67.68% 74.88% +7.2
% of p character of H
10
32.32% 25.12% 7.2
q (O
9
)/e 0.6737 0.6701 +0.0036
q (H
10
)/e 0.4890 0.4653 0.0237
sp
n
(C7 O
8
) sp
1.97
sp
2.48
s
% of s character 33.58% 28.67% 4.91
% of p character of C7 35.04% 32.82% 2.22
% of p character of O
8
64.96% 67.18% +2.22
q(C7)/e 0.8019 0.8650 +0.0631
q(O
8
)/e 0.5757 0.6793 0.1036
sp
n
(C7 O
9
) sp
2.60
sp
2.54
+s
% of s character 27.69% 28.16% +0.47
% of p character of C7 32.12% 33.37% +1.25
% of p character of O
9
67.88% 66.63% 1.25
q(C7)/e 0.8019 0.8650 +0.0631
q(O
9
)/e 0.6737 0.6701 +0.0036
sp
n
(N
11
O
12
) sp
2.13
Sp
2.12
+s
% of s character 31.90% 31.99% +0.09
% of p character of N
11
40.26% 49.00% +8.74
% of p character of O
12
59.74% 51.00% 8.74
q(N
11
)/e 0.4885 0.4903 +0.0018
q(O
12
)/e 0.3622 0.3539 +0.0083
n
2
(O
9
) *(C
7
O
8
) and n
1
(O
21
) *(C
22
O
23
) are obtained as
8.49, 39.49 and 23.30kcal mol
1
. In addition, the s character of sp
n
hybrid orbital for the C
7
O
8
bond decreases from sp
1.97
to sp
2.48
upondimerizationsubstantiates the weakening of C
7
O
8
bondand
its elongation.
4.3. Molecular electrostatic potential (MEP) surface
For investigating chemical reactivity of the molecule, molecular
electrostatic potential (MEP) surface is plotted over the optimized
electronic structure of NTA using density functional B3LYP method
with 6-311++G(d,p) basis set. The MEP generated in space around a
molecule by the charge distribution is very helpful in understand-
ing the reactive sites for nucleophilic and electrophilic attack in
hydrogen bonding interactions [32] and in biological recognition
process [33]. In hydrogen bonded systems, the study of interacting
behavior of various constituents of the molecule has great impor-
tance. Because the computationally or experimentally observed
MEP surface is directly provide information about the electrophilic
(electronegative charge region) and nucleophilic (most positive
charge region) regions. Fig. 4 shows the computationally observed
MEP contour map along with the tting point charges to the elec-
trostatic potential v( r). The electrostatic potential v( r) at any point
in space around a molecule by charge distribution is given by
v( r) =

/
Z
/

R
/
r

( r)dr

r r

(1)
where ( r) is the electron density function of the molecule, Z
A
is
the charge on the nucleus A located at

R
/
and r is the dummy inte-
gration variable. In the contour map, the regions with red colours
areregardedas most electronegative(electrophilic) regions andthe
regions with blue colours are most positive (nucleophilic) regions,
whereas the bluish green colours surrounded by the ring systemof
NTA are related to less positive regions.
In Fig. 4, there are several possible sites for the electrophilic
attacks over the oxygen atoms; O
8
, O
9
, O
12
and O
13
. The aver-
age maximum negative electrostatic potential values for these
electrophilic sites calculated at B3LYP/6-311++G(d,p) is about
22.2920a.u. The tting point charges to those electrostatic poten-
tials are calculated as 0.6410 (O
9
), 0.6398 (O
8
), 0.4671 (O
13
)
142 V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147
Fig. 4. Molecular electrostatic potential surface (left) and the point charges, electric potential values (right) on each atomof 6-nitro-m-toluic acid. (For interpretation of the
references to color in the text, the reader is referred to the web version of the article.)
and 0.4485e (O
12
). In the title molecule, all the hydrogen atoms
anda methyl groupconnectedto the ring systemof benzene having
less positive charges. Besides, the hydrogen atomH
10
(0.4129e) is
surrounded by most nucleophilic region. Similarly, the tting point
charge corresponding to N
11
atom is reported as high positive as
0.7573e, but MEP map seems yellowcoloredonN
11
. This is because
of the fact that, most of the electrophilic regions are surrounded by
N
11
atom.
4.4. Frontier molecular orbitals
The most important frontier molecular orbitals (FMOs) such as
highest occupiedmolecular orbital (HOMO) andlowest unoccupied
molecular orbital (LUMO) plays a crucial part inthe chemical stabil-
ity of the molecule [34]. The HOMOrepresents the ability to donate
anelectronandLUMOas anelectronacceptor represents the ability
to accept an electron. The energy gap between HOMO and LUMO
also determines the chemical reactivity, optical polarizability and
chemical hardness-softness of a molecule [35].
In the present study, the HOMO and LUMO energies are pre-
dicted at B3LYP method with 6-311++G(d,p) basis set. According
to the results, the NTA molecule contains 47 occupied molecular
orbitals and247 unoccupiedvirtual molecular orbitals. Fig. 5 shows
the distributions and energy levels of HOMO1, HOMO, LUMO
and LUMO+1 orbitals for the stable monomer of NTA molecule
in gaseous phase. It is clear from Fig. 5 that the isodensity plots
for the HOMO and HOMO1 are well localized within the ring
whereas, the orbital overlapping on the ring system of LUMO
surface shows empty. LUMO+1 orbital of the title molecule is com-
pletely delocalized the entire part of the molecule. Commonly, the
atom occupied by more densities of HOMO should have stronger
ability to detach an electron whereas; the atom with more occu-
pation of LUMO should have ability to gain an electron [36]. For
NTA molecule, the HOMO orbital of type is lying at 0.2856a.u
and HOMO1 orbital of type is lying at 0.2926a.u. while the
LUMOand LUMO+1 orbitals are * in type and are lying at 0.1063
and 0.0672a.u., respectively. As a result, a very small energy gap is
observed between HOMOand LUMOmolecular orbitals of NTAand
the energy gap calculated at B3LYP/6-311++G(d,p) is 0.1793a.u..
Hence the probability of * proton transition is highly possible
in between HOMO and LUMO orbitals for the NTA.
The chemical hardness and softness of a molecule is a good
indicator of the chemical stability of a molecule. From the
HOMOLUMO energy gap, one can nd whether the molecule is
hard or soft. The molecules having large energy gap are known as
hard and molecules having a small energy gap are known as soft
molecules. The soft molecules are more polarizable than the hard
ones because they need small energy to excitation. The hardness
value of a molecule can be determined by the formula [37]:
q =
(
HOMO
+
LUMO
)
2
(2)
where
HOMO
and
LUMO
are the energies of the HOMO and
LUMO orbitals. The value of q in the title molecule is 0.0897a.u..
hence from the calculation, we conclude that the molecule taken
for investigation belongs to soft material and the polarizabil-
ity of the title molecule calculated at B3LYP/6-311++G(d,p) is
111.879810
30
esu.
4.5. Vibrational spectra
The investigation of vibrational wavenumbers of the chemical
compounds have been put a primary role in the spectral analy-
sis. In the spectroscopic eld, the vibrational spectra of substituted
benzene derivatives have been greatly investigated by various
spectrocopists. Because, a single substitution can have a tendency
to put greater changes in the vibrational wavenumbers of benzene.
In other words, the molecular systemof benzene is greatly affected
by the nature of the substituents.
In order to obtain the spectroscopic signature, the experimen-
tal FT-IR and FT-Raman spectra are being recorded on the solid
phase of NTA molecule. Moreover, the theoretical frequency calcu-
lation is also performed on the gaseous phase of the molecule using
density functional B3LYP method with 6-311++G(d,p) basis set. As
a result, the present molecule holds 54 harmonic wavenumbers
under C1 point group symmetry. Due to the neglect of anharmonic-
ityeffect at the beginningof frequencycalculation, the theoretically
computed wavenumbers are found to be somewhat in disagree-
ment with that of the experimental. To overcome the discrepancies
between observed and calculated wavenumbers, six different scale
factors are introduced. In the present study, the scaled theoretical
wavenumbers are compared with that of experimental wavenum-
bers (Table5). For comparativepurpose, thetheoreticallysimulated
V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147 143
Fig. 5. Electron density surface plots for the most important frontier molecular orbitals with their energies (a.u) of 6-nitro-m-toluic acid.
Fig. 6. (a) Experimental FT-IR and (b) simulated infrared spectra of 6-nitro-m-toluic acid.
144 V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147
Table 5
Vibrational wavenumbers, IR intensities, Raman intensities and vibrational assignments corresponding to the normal modes associated with 6-nitro-m-toluic acid.
Modes Experimental wavenumbers Theoretical
wavenumbers (cm
1
)
B3LYP/6-311++G(d,p))
Scale factors IR intensity Raman
intensity
Vibrational assignments
a
(% PED)
FT-IR FT-Raman Unscaled Scaled
1. 3563 vw 3759 3571 0.950 105.5 6.1 DOH(100)
2. 3077 m 3073 m 3214 3085 0.960 1.1 6.0 DringCHss(97)
3. 3033 vw 3184 3057 0.960 1.2 4.2 DringCHss(97)
4. 2976 w 2976 w 3178 2987 0.940 6.9 6.7 DringCHass(98)
5. 2934 w 2927 m 3114 2927 0.940 12.8 4.7 DmethylCHass(96)
6. 2889 m 2880 vw 3084 2899 0.940 10.2 6.6 DmethylCHass(99)
7. 2804 w 2805 w 3030 2848 0.940 14.1 23.2 DmethylCHss(100)
8. 1697 vs 1805 1697 0.940 360.1 11.9 DC O(67), OH(22)
9. 1612 vs 1644 1611 0.980 13.8 16.9 DCC(61), CN(23)
10. 1591 ms 1596 s 1627 1594 0.980 65.5 13.2 DCC(50), CH(22), CN(16)
11. 1510 w 1587 1508 0.950 262.9 4.7 DasNO
2
(56), CN(16), DCC(12)
12. 1477 w 1482 m 1512 1481 0.980 1.3 3.2 DCC(42), CH(27), CH
3
(13)
13. 1462 vw 1496 1466 0.980 6.5 2.0 CH
3
(61), CH(17)
14. 1433 s 1487 1428 0.960 8.0 3.3 CH
3
(77)
15. 1386 m 1389 w 1436 1379 0.960 40.2 2.4 DCC(46), CH(21), CH
3
(14)
16. 1348 vs 1346 vs 1416 1345 0.950 2.5 8.7 CH
3
(64), CH(10)
17. 1306 s 1382 1313 0.950 315.8 61.3 DsNO
2
(58), CO(18), DCN(16)
18. 1360 1292 0.950 53.7 2.7 OH(47), CH(20),DCC(16)
19. 1343 1276 0.950 5.3 2.0 DCC(51),CH
3
(18), OH(11)
20. 1269 s 1265 vw 1299 1260 0.970 0.8 0.6 CH(62), OH(18)
21. 1198 vw 1245 1183 0.950 38.6 13.0 DCC(50), CH(19), OH(13)
22. 1161 w 1167 vw 1187 1151 0.970 157.5 1.8 CH(54), DCC(21)
23. 1141 w 1142 ms 1178 1142 0.970 15.3 5.7 CH(49), DCC(25)
24. 1076 w 1080 vw 1142 1084 0.950 90.7 7.4 DCO(45), CH(21), CO(16)
25. 1041 w 1043 vw 1085 1042 0.960 22.4 10.7 DCN(41), CH(20), CO(17)
26. 1025 vw 1062 1020 0.960 8.2 0.3 CH
3
(58), CH(17)
27 977 vw 1021 980 0.960 4.0 1.0 CH
3
(63), ring(15)
28 920 m 985 926 0.940 1.5 0.1 CH(78)
29 891 ms 895 m 924 896 0.970 4.0 0.4 CH(65)
30 843 vs 918 849 0.925 11.2 10.0 NO
2
(53), ring(19), DCC(14)
31 856 820 0.960 24.1 2.7 CH(62), NO
2
(19)
32 785 vw 784 w 851 790 0.930 32.0 3.4 DCC(48), CH(12)
33 743 m 798 742 0.930 12.8 3.0 DCC(48), ring(15), OH(12)
34 740 w 768 737 0.960 40.9 0.8 NO
2
(55), CH(22), CCO(14)
35 703 w 733 704 0.960 10.4 14.3 COOH(51), ring (24)
36 674 s 673 w 704 676 0.960 4.1 1.6 CCC(46), OH(20), ring(17)
37 616 ms 648 622 0.960 27.9 2.4 COH(47), ring(25)
38 602 w 633 608 0.960 20.6 4.3 CCC(40), ring(19), CH(12)
39 585 w 601 583 0.970 70.0 5.5 OH(67), ring(18)
40 562 w 593 569 0.960 2.8 2.4 NO
2
(49), ring (20), CCC(13)
41 541 w 563 540 0.960 21.8 1.1 COOH(52), ring(12)
42 420 w 440 422 0.960 4.6 1.6 COH(41), CH(19), ring(15)
43 377 vw 393 377 0.960 4.7 11.6 CCC(39), ring(22), COOH(18)
44 380 365 0.960 3.0 4.9 C NO
2
(45), ring(17), COOH(13)
45 350 336 0.960 0.9 1.7 CCC(42), COOH(19), ring(15)
46 329 316 0.960 1.1 5.0 ring(50)
47 242 vw 261 251 0.960 0.7 10.0 ring(51)
48 205 w 207 199 0.960 0.3 8.0 ring (45), CH
3
(18), NO
2
(12)
49 178 171 0.960 2.8 14.5 C NO
2
(53), COH(26)
50 118 w 134 129 0.960 1.6 26.3 ring(50), NO
2
(19), COH(17)
51 99 95 0.960 2.0 45.3 ring(52), COH(21)
52 93 89 0.960 0.2 60.5 ring(65)
53 43 41 0.960 0.1 76.7 CH
3
(90)
54 32 31 0.960 1.7 100.0 NO
2
(45), COH(37)
a
Ds, symmetry stretching; Das, asymmetry stretching; , in-plane bending; , out-of-plane bending; , methyl in-plane ricking; , methyl out-of plane rocking; , NO
2
scissoring; , NO
2
wagging; , NO
2
rocking; and , torsion.
scaled IR and Raman spectra are being presented in Figs. 6 and 7
along with their experimental FT-IR, FT-Raman spectrum respec-
tively. The detailed descriptions for the vibrational assignments
of various functional groups of NTA molecule are summarized as
follows.
4.5.1. Aromatic C H vibrations
In the present study, the three hydrogen atoms (H
14
, H
15
and
H
20
), which are attached to the benzene ring of NTA give rise to
three C H stretching modes (2 4), three C H in-plane bend-
ing (20, 22, 23) and three C H out-of-plane bending (28, 29,
31) modes. Usually the heteroaromatic organic molecule shows
the presence of the C H stretching vibrations in the wavenumber
region 30003100cm
1
and it is the characteristic region for the
identication of C H stretching vibrations [38]. For NTA molecule,
the aromatic C Hstretching modes are assigned to 3077, 3033 and
2976cm
1
in FT-IR, and 3073 and 2976cm
1
in FT-Raman. The
scaled theoretical wavenumbers at B3LYP/6-311++G(d,p) method
for C H stretching modes are in agreement with the experimen-
tal wavenumbers and potential energy distribution (PED) results
showed that, these modes are very pure. For toluic acid (TA), the
bands at 3080, 3030 and 3020cm
1
in FT-IR and 3050, 3030cm
1
V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147 145
Fig. 7. (a) Experimental FT-Raman and (b) simulated Raman spectra of 6-nitro-m-toluic acid.
in FT-Raman have been assigned as C Hstretching modes by Babu
et al. [14]. In our previous work, we have assigned 3095, 3060cm
1
inFT-IRand3054cm
1
inFT-Ramanbands as C Hstretchingmodes
of 5-nitrosalicylic acid (also known as 2-hydroxy-5-nitro benzoic
acid) [39].
In aromatic compounds, the C H in-plane and out-of-plane
bending vibrations appear in the range 10001300cm
1
and
7501000cm
1
[40,41], respectively. Hence the C H in-plane
bending modes of the title molecule are attributed to 1269,
1161 and 1141cm
1
in FT-IR and 1265, 1167 and 1142cm
1
in
FT-Raman. For TA, the aromatic C H in-plane bending modes
were assigned to 1200, 1120 and 1090cm
1
in FT-IR and 1160,
1120cm
1
in FT-Raman [14]. The percentage of PED depicted in
the last column of Table 5 shows that, O H in-plane bending and
C C stretching vibrations are interacting considerably with C H
in-plane bending mode.
The mediumbands observed at 920, 895cm
1
in FT-Raman and
at 891cm
1
in FT-IR are ascribed to C H out-of plane bending
modes of the title molecule. Thus the scaled theoretical wavenum-
bers of C H out-of plane bending modes depicted in Table 5 are
found to be in agreement with the experimental data of NTA as
well as the similar kind of molecules [2,14].
4.5.2. Methyl group vibrations
A single methyl substitution on the benzene ring of the title
molecule consists of nine fundamental vibrational modes. Nor-
mally, the C H stretching modes of the methyl group produce
bands inthe region28402975cm
1
[42,43]. For the title molecule,
the bands observed at 2934, 2889 and 2804cm
1
in FT-IR and
2927, 2880 and 2805cm
1
in FT-Raman are attributed to C H
stretching mode of the methyl group. The percentage of PEDshows
that, the methyl C Hstretching modes are pure like aromatic C H
stretching. In the case of TA, the bands present at 2960, 2930 and
2890cm
1
in FT-IR have been assigned as C Hstretching modes of
the methyl group.
A prominent intensity band at 1348cm
1
in FT-IR and the bands
at 1462, 1346cm
1
in FT-Raman are assigned to in-plane bend-
ing modes of the methyl group. The strong band at 1433cm
1
in FT-IR corresponding to mode 14 is assigned to out-of plane
bending mode of the methyl group. Generally aromatic com-
pound displays the methyl in-plane (CH
3
) and out-of plane
(CH
3
) rocking vibration bands in the neighborhood of 1045cm
1
and 97070cm
1
, respectively [44]. In the present study, the
band present at 1025cm
1
in FT-Raman and the weak band at
977cm
1
in FT-IR are assigned to in-plane and out-of-plane rock-
ing vibrations, respectively. The calculated value of 41cm
1
at
B3LYP/6-311++G(d,p) method is assigned to the twisting mode of
the methyl group (zCH
3
).
4.5.3. Carboxyl group vibrations
The vibrational assignments of carboxylic acid group of the title
molecule have great deal of interest. In view of the fact that, the
dimeric entities of the molecule is possible to exist via carboxylic
acidgroup. Nevertheless, thederivatives of carboxylic acids arebest
characterized by the carbonyl and hydroxyl groups. In particular,
the presence of carbonyl group is most important in the infrared
spectrumbecause of its strong intensity of absorptionandhighsen-
sitivity toward relatively minor changes in its environment. Intra-
and intermolecular hydrogen bonding interactions affect the car-
bonyl absorptions incommonorganic compounds due toinductive,
mesomeric, eld and conjugation effects [45].
The characteristic infrared absorption wavenumber of C O in
acids are normally strong in intensity and are found in the region
16901800cm
1
[20,38]. In the present study, the strong band at
1697cm
1
in FT-IR is assigned to C O stretching. The calculated
value of this mode at B3LYP/6-311++G(d,p) method is found to be
in consistent with the experimental data. For TA, the FT-IR band
observed at 1690cm
1
has been assigned as C O stretching mode
[14]. For 5-NSA, the strong band at 1665cm
1
in FT-IR and band at
1657cm
1
in FT-Raman were assigned to C O stretching [39].
A band related to C O stretching mode of carboxylic acid group
is highly coupled with the vibrations of adjacent groups or atoms.
Hence the wavenumber region for the existence of C O is based
on the nature of the nearby substitution. In the title molecule, the
weak band at1076cm
1
in FT-IR and 1080cm
1
in FT-Raman are
assigned to C O stretching mode. For TA, the band at 1270cm
1
146 V. Balachandran et al. / Spectrochimica Acta Part A 92 (2012) 137147
in FT-Raman has been assigned to C O stretching mode [14]. The
C O stretching mode normally appears in the frequency region
12001300cm
1
. In the present study, the assignment this mode
is somewhat lower than that of the literature [14]. The inter-,
intramolecular hydrogen bonding interactions and delocalization
of ED from O
8
to C
7
O
9
and O
23
H
24
may cause a change in the
characteristic frequency of C Ostretching mode. The O Hstretch-
ing vibrations are characterized by a very broad band appearing in
the region 34003600cm
1
[20]. In the present study, the band
for this mode is not active in FT-Raman spectrum. Hence the band
observedat 3563cm
1
inFT-IRis assignedtoO Hstretching mode.
The scaled theoretical wavenumbers of C O and O H stretching
modes at B3LYP/6-311++G(d,p) in the title molecule are matched
well with the experimental value as well as the similar kind of
molecules. In the case of NTA, the in-plane and out-of-plane bend-
ing vibrations are assigned to the modes 35, 37, 41 and 42. The
predicted wavenumbers related to these modes are found to be in
agreement with their experimental observations.
4.5.4. NO
2
vibrations
Usually, a single nitro group substitution linked with the ben-
zene ring provides us six vibrations viz. symmetry stretching,
asymmetry stretching, scissoring, wagging, rocking and twist-
ing. The asymmetric and symmetric stretching vibrations of NO
2
normally produce bands in the regions 15001570cm
1
and
13001370cm
1
in nitro benzenes and substituted nitro ben-
zenes [46], respectively. In the title molecule, the NO
2
asymmetric
stretching is observed at 1510cm
1
in FT-Raman. The strong inten-
sity band observed at 1306cm
1
in FT-IR is assigned to NO
2
symmetry stretching. The theoretically scaled values at 1508 and
1313cm
1
by B3LYP/6-311++G(d,p) methodare incorrelationwith
the experimental observations of NO
2
asymmetry and symmetry
stretching vibrations, respectively.
Nitrosubstitutedaromatic compounds generateabandof weak-
to-medium intensity in the low frequency region belongs to NO2
bending vibrations [47,48]. It follows fromTable 5 that the strong
intensity band observed at 843cm
1
in FT-IR is designated as NO
2
scissoring (NO
2
) to the mode 30. NO
2
wagging and rocking
modes of the title molecule display the bands at 740cm
1
in FT-IR
and 562cm
1
in FT-Raman. It should be mentioned that, the scaled
wavenumbers calculatedat B3LYP/6-311++G(d,p) methodarecoin-
cide well with their experimental datas. The scaled wavenumber
31cm
1
assigned to NO
2
torsion mode of the title molecule is in
agreement with the assignments proposed by Kanna Rao and Syam
Sundar [49].
4.5.5. C N vibrations
The bond between C
2
atomof the benzene ring and N
11
atomof
the nitro group gives rise to three vibrational modes; C N stretch-
ing (DCN), C N in-plane bending (C NO
2
) and C N out-of plane
bending (C NO
2
) vibrations. Generally, the identication of C N
bands in both the FT-IR and FT-Raman spectra are rather a difcult
task, since these bands are highly mixed with other vibrations. In
the present study, the weak intensity band at 1041cm
1
in FT-IR
and 1043cm
1
in FT-Raman is assigned to C N stretching mode of
NTA. In previous, we have reported C N stretching at 928cm
1
in
FT-Raman for 5-nitrosalicylic acid [39]. The peaks corresponding to
C N in-plane and out-of-plane bending modes of the investigated
compound are not observed in both FT-IR and FT-Raman spectrum.
Hence with the aid of PED results, the calculated values of 365 and
171cm
1
are assigned to C N in-plane and out-of plane bending
modes, respectively. For 5-NSA, these bands have been assigned at
350 (C NO
2
) and 158cm
1
(C NO
2
).
4.5.6. Ring vibrations
In case of NTA, the carbon atoms coupled together in the hexag-
onal chain of benzene possesses six C C stretching vibrations in
the region of 14601150cm
1
. According to the PED results, the
ring C C stretching modes are observed at 1612, 1591, 1477 and
1386cm
1
in FT-IR and 1596, 1482, 1389, and 1198cm
1
in FT-
Raman for NTA. The in-plane and out-of-plane bending vibrations
of benzene ring are generally observed below 1000cm
1
[44] and
these modes are not pure but they contributes drastically from
other vibrations andare substituent-sensitive. Inthe title molecule,
ring in-plane (ring) and out-of plane (ring) bending modes are
affected to a great extent by the substituents and produce bands
below 500cm
1
. The weak intensity bands present at 242 and
118cm
1
in FT-Raman spectrumare assigned to ring and a band
observed at 205cm
1
is assigned to ring. The scaled theoretical
wavenumbers corresponding to ring vibrations are found to have a
good correlation with their available experimental observations.
5. Conclusions
In the present study, the potential energy surface of 6-nitro-m-
toluic acid was examined. The optimized geometrical parameters
of the minimum energy conformer obtained from the relaxed
scan were computed by density functional B3LYP method with
6-311++G(d,p) basis set. The optimized geometrical parameters
of the dimer conformer of NTA were compared with that of the
monomer. The signicant changes in bond lengths of the monomer
upon dimerization were explained with the help of NBO analysis.
The delocalization of ED from Lewis base to Lewis acid sites were
discussed with their stabilization energies. The reported natural
atomic hybrid orbitals of interacting NBOs of the molecule allowed
us to knowabout the lengthening and shortening of O H and C O
bonds.
The mapped isodensity surfaces for the frontier molec-
ular orbitals were plotted. The smallest energy gap
(z
HOMOLUMO
=0.1793a.u.) between HOMO and LUMO orbitals
revealed that the molecule used in this study belongs to soft
material and the probability of * proton transition is highly
possible within the molecule. In addition, the nucleophilic and
electrophilic sites on the MEP surface were determined. The
charges accumulated on various constituents of MEP surface
were reported along with their electric potential values. The
detailed descriptions for the vibrational normal modes of NTA
molecule were presented on the basis of combined experimental
and theoretical IR and Raman studies. The scaled theoretical
wavenumbers computed at B3LYP/6-311++G(d,p) method were
found in agreement with their experimental observations.
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