Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Electronic [UVVisible] and vibrational [FT-IR, FT-Raman] investigation

and NMRmass spectroscopic analysis of terephthalic acid using
quantum Gaussian calculations
N. Karthikeyan a, J. Joseph Prince b, S. Ramalingam c,, S. Periandy d
a

Department of Physics, Indra Ganesan College of Engineering, Tiruchirappalli, Tamilnadu, India

Department of Physics, Anna University, BIT Campus, Tiruchirappalli, Tamilnadu, India
Department of Physics, A.V.C. College, Mayiladuthurai, Tamilnadu, India
d
Department of Physics, Tagore Arts College, Puducherry, India
b
c

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 The calculations were carried out at

The molecular mass spectral data related to base molecule and substitutional group of the compound was
analyzed. The modication of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the benzene ring was investigated and it is displayed in the following gure. The orbital
energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. The interaction over the frontier molecular orbitals the possibility of electrophilic and nucleophilic hit is also
presented in the gure. The present molecule was fragmented with respect to atomic mass and the mass
variation depends on the substitutions have also been studied.

HF, B3LYP and B3PW91 methods.

 The NLO, optical properties, ESP, ED
and the MEP were analyzed.
 The vibrational spectra and UV
Visible showed the change of
electronic conguration.
 The calculated data are compared
with experimental data.

a r t i c l e

i n f o

Article history:
Received 16 September 2014
Received in revised form 19 November 2014
Accepted 25 November 2014
Available online 24 December 2014
Keywords:
Terephthalic acid
Dicarboxylic group
Optical properties
Hybrid Gaussian
NLO activity
FMO

a b s t r a c t
In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid
(TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical
and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data
related to base molecule and substitutional group of the compound was analyzed. The modication of
the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The 13C and 1H NMR spectra were simulated by using the gauge independent
atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with
experimental spectra. The study on the electronic and optical properties; absorption wavelengths,
excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid
Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were

Corresponding author. Tel./fax: +91 04364 225367.

E-mail address: ramalingam.physics@gmail.com (S. Ramalingam).
http://dx.doi.org/10.1016/j.saa.2014.11.112
1386-1425/Crown Copyright 2014 Published by Elsevier B.V. All rights reserved.

230

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

calculated and the molecular orbital lobe overlapping showed the inter charge transformation between
the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to
atomic mass and the mass variation depends on the substitutions have also been studied.
Crown Copyright 2014 Published by Elsevier B.V. All rights reserved.

Introduction
The terephthalic acid (benzene-1,4-dicarboxylicacid) is a
organic colorless solid compound which is produced by oxidation
of p-xylene with dilute nitric acid. Terephthalic acid is a commodity chemical and is used principally as a precursor to the polyester
PET, used to make clothing and plastic bottles. Polyester bers
based on terephthalic acid provide easy fabric care, both alone
and in blends with natural and other synthetic bers. Generally,
polyester lms are used widely in audio and video recording tapes,
data storage tapes, photographic lms, labels and other sheet
material requiring both dimensional stability and toughness. Terephthalic acid derivative, polyethylene terephthalate (PET), has
become the primary container resin for applications such as carbonated beverage bottles, while other polyterephthalates provide
dimensional stability, good heat resistance and durability for engineering applications [1].
The terephthalic acid is used in the paint as a carrier and it is
also used in the pharmaceutical industry as a raw material for certain drugs. In addition to these end uses, terephthalic acid based
polyesters and polyamides are also used in hot melt adhesives.
Terephthalic acid is an important raw material for lower molecular
weight saturated polyesters for powder and water-soluble coatings. There is a smaller, but nevertheless signicant, demand for
terephthalic acid in the production of polybutylene terephthalate
and several other engineering polymers [2]. In the research laboratory, terephthalic acid is popularized as a component for the synthesis of metalorganic frameworks. However, so far, after the
careful screening on literature, it is found that no research article
was published on such a molecule with experimental and computational calculations and no electronic structure study has been
carried out. In this present work, a detailed vibrational, electronic,
NMR and mass spectroscopic investigation and frontier molecular
studies and Kubo gap analysis on terephthalic acid have been carried out.

B3PW91/6-31++G(d,p)/6-311 + G(d,p) basis set, the scaling factors

are 0.908,0.955, 0.970, 1.04 and 1.15/0.908, 0.960, 1.04 and 1.15.
The observed (FT-IR and FT-Raman) and calculated vibrational frequencies and vibrational assignments are submitted in Table 2.
Experimental and simulated spectra of IR and Raman are presented
in the Figs. 2 and 3, respectively.
The 1H and 13C NMR isotropic shielding are calculated with the
GIAO method [11] using the optimized parameters obtained from
B3LYP/6-311++G(d,p) method. 13C isotropic magnetic shielding
(IMS) of any X carbon atoms is made according to value 13C IMS

Fig. 1. Molecular structure of terephthalic acid.

Computational prole
Generally, the hand-in-hand investigation of vibrational spectroscopy along with quantum mechanical calculations is a powerful tool for the thoughtful of fundamental vibrational behavior of a
molecule. In the present work, some of the hybrid methods; LSDA,
B3LYP and B3PW91 are carried out using the basis sets of 631++G(d,p) and 6-311++G(d,p). All these calculations are performed using GAUSSIAN 09 W [3] program package on Pentium core
i3 processor in personal computer. In DFT methods; Beckes three
parameter hybrids function combined with the LeeYangParr correlation function (B3LYP) [4,5], Beckes three parameter exact
exchange-function (B3) [6] combined with gradient-corrected correlational functional of Lee, Yang and Parr (LYP) [7,8] and Perdew
and Wang (PW91) [9,10] predict the best results for molecular
geometry and vibrational frequencies for moderately larger molecules. The calculated frequencies are scaled down to yield the
coherent with the observed frequencies. The scaling factors for
B3LYP/6-31++G(d,p) basis set are 0.916, 0.955 and 1.14, the scaling
factors for B3LYP/6-311++G are 0.915, 0.962, 1.04 and 1.14. For

Fig. 2. Experimental [A] and calculated [BD] FT-IR spectra of terephthalic acid.

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

231

true energy is different for different methods. Though, the molecule contains couple of carboxyl groups, the entire atoms of the
molecule belong to same plane. The hexagonal structure of the
base molecule is broken due to the injection of coupling of COOH
groups in to the ring. All the CC bonds in the ring are little
expanded depending upon the substitutional penetration of the
carboxylic groups. Particularly, the bonds C1C2; C1C6 and C3
C4; C4C5 are equally and more stretched out than other CC
bonds. The entire CH bonds in the ring having almost equal inter
nuclear distance. Form the optimized molecular structure; it is
observed that the ring accepts functional group and simultaneously altered its conguration. The bond angles C2C1C6 and
C3C4C5 of are little expanded due to the presence of COOH
group at top and bottom of in the parental molecule.

Vibrational assignment

Fig. 3. Experimental [A] and calculated [BD] FT-Raman spectra of terephthalic

acid.

of TMS, CSX = IMSTMSIMSx. The 1H and 13C isotropic chemical

shifts of TMS at B3LYP methods with 6-311++G(d,p) level using
the IEFPCM method in DMSO and CCl4. The absolute chemical shift
is found between isotropic peaks and the peaks of TMS [12].
The electronic properties; HOMOLUMO energies, absorption
wavelengths and oscillator strengths are calculated using B3LYP
method of the time-dependent DFT (TD-DFT) [13,14], basing on
the optimized structure in gas phase and solvent [DMSO, ethanol,
methanol and acetone] mixed phase. Thermodynamic properties
have been calculated at 298.15 C in gas phase using B3LYP/6311++G(d,p) method. Moreover, the dipole moment, nonlinear
optical (NLO) properties, linear polarizabilities and rst hyperpolarizabilities and chemical hardness have also been studied.
Experimental details
The FT-IR, FT-Raman, 13C and 1H NMR and mass spectra of terephthalic acid were recorded in respective instruments which were
purchased from SigmaAldrich Chemicals USA and cooperated
with National Institute of Standards and Technology [NIST], US
Department of Commerce.
Results and discussion
Molecular geometry
The molecular structure of terephthalic acid belongs to C2V
point group symmetry. The molecular structure is optimized by
Bernys optimization algorithm using Gaussian 09 and Gauss view
05 programs and is shown in Fig. 1. The comparative optimized
structural parameters such as bond length, bond angle and dihedral angle are presented in Table 1. The present molecule consists
of benzene ring along with two carboxyl groups.
The structure optimization and zero point vibrational energy of
the compound in DFT (B3LYP/B3PW91) with 6-31++G(d,p) and 6311++G(d,p) are 81.86, 81.61, 82.22, 81.98 and 101.03 Kcal/mol,
respectively. The calculated energy by B3LYP/6-311++G(d,p)
method is lower than the energy calculated by other methods
because the assumption of ground state energy corresponding to

In order to obtain the spectroscopic signature of the TA, the

computational calculations are carried out for frequency analysis.
The molecule is indentied with CS point group symmetry, consists
of 18 atoms, so it has 48 normal vibrational modes. On the basis of
C2V symmetry, the 48 fundamental vibrations of the molecule can
be distributed as

C Vib 19A1 7A2 8B1 14B2

A1 and B2 irreducible representations correspond to stretching,
ring deformation and in plane bending vibrations while A2 and B1
correspond to ring, torsion and out of plane bending vibrations.
The harmonic vibrational frequencies (unscaled and scaled) calculated at B3LYP and B3PW91 levels using the triple split valence
basis set along with the diffuse and polarization functions; 631++G(d,p) and 6-311++G(d,p) and observed FT-IR and FT-Raman
frequencies for various modes of vibrations have been presented
in Tables 2 and 3. Comparison of calculated frequencies with the
experimental values reveal the over estimation of the calculated
vibrational modes due to the neglect of a harmonicity and change
of state of real system.

CH vibrations
Generally, the benzene derivative compounds have consecutive
peaks in the region 31003000 cm1 owing to CH stretching
vibrations [1517]. In this case, the peaks with weak in IR and
medium and very strong intensity in Raman are observed at
3100, 3095, 3085 and 3060 cm1 assigned to CH ring stretching
vibrations. As predictable, these four fundamental modes are
uncontaminated stretching modes. In addition to that, the IR bands
are weak whereas the Raman bands are medium and very strong.
Among four, three CH stretching bands are found at top end of
the expected range since these have not been affected due to other
vibrations.
The CH in plane ring bending vibrations normally observed as
a number of strong to weak intensity sharp bands in the region
13001000 cm1 [18]. In the present compound, the CH in plane
bending vibrations found at 1185, 1140, 1125 and 1020 cm1. Most
of the bands are strong and the peaks are found in IR and Raman
equally. Normally, the CH out of plane bending vibrations are
appeared in the region 950780 cm1 [19,20]. In this case, the C
H out of plane bending bands are identied at 880, 835, 820 and
805 cm1. Like in plane bending, all the bands are observed at
the middle of the expected region. The assigned frequencies for
CH vibrations are found to be well within their characteristic
regions and it is conclude that CH vibrations are pure and have
not been affected by other vibrations.

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N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

Table 1
Optimized geometrical parameters for terephthalic acid computed at LSDA, B3LYP and B3PW91 with 6-31++G(d,p) and 6-311++G(d,p) basis sets.
Geometrical parameters

Computational methods
LSDA

B3LYP

B3PW91

6-31++G(d,p)

6-311++G(d,p)

6-31++G(d,p)

6-311++G(d,p)

6-31++G(d,p)

6-311++G(d,p)

Bond length ()
(C1C2)
(C1C6)
(C1C11)
(C2C3)
(C2H7)
(C3C4)
(C3H8)
(C4C5)
(C4C15)
(C5C6)
(C5H9)
(C6H10)
(C11O12)
(C11O13)
(O13H14)
(C15O16)
(C15O17)
(O17H18)

1.396
1.396
1.471
1.386
1.094
1.396
1.094
1.396
1.471
1.383
1.096
1.096
1.217
1.345
0.983
1.217
1.345
0.983

1.391
1.391
1.470
1.381
1.092
1.391
1.092
1.391
1.470
1.378
1.094
1.0941
1.209
1.342
0.979
1.209
1.342
0.979

1.402
1.403
1.490
1.393
1.083
1.402
1.083
1.403
1.490
1.390
1.084
1.084
1.215
1.357
0.971
1.215
1.357
0.971

1.399
1.399
1.490
1.390
1.081
1.399
1.081
1.399
1.490
1.387
1.082
1.082
1.207
1.356
0.968
1.207
1.356
0.968

1.400
1.400
1.487
1.391
1.084
1.400
1.084
1.400
1.487
1.388
1.085
1.085
1.213
1.351
0.969
1.213
1.351
0.969

1.396
1.397
1.486
1.387
1.083
1.396
1.083
1.397
1.486
1.384
1.083
1.083
1.206
1.349
0.967
1.206
1.349
0.967

Bond angle ()
(C2C1C6)
(C2C1C11)
(C6C1C11)
(C1C2C3)
(C1C2H7)
(C3C2H7)
(C2C3C4)
(C2C3H8)
(C4C3H8)
(C3C4C5)
(C3C4C15)
(C5C4C15)
(C4C5C6)
(C4C5H9)
(C6C5H9)
(C1C6C5)
(C1C6H10)
(C5C6H10)
(C1C11O12)
(C1C11O13)
(O12C11O13)
(C11O13H14)
(C4C15O16)
(C4C15O17)
(O16C15O17)
(C15O17H18)

120.700
121.69
117.609
119.614
119.214
121.171
119.614
121.171
119.214
120.700
121.69
117.609
119.685
118.104
122.210
119.685
118.104
122.210
124.614
113.035
122.350
105.835
124.614
113.035
122.350
105.835

120.642
121.762
117.595
119.643
119.164
121.191
119.643
121.191
119.164
120.642
121.762
117.595
119.713
118.091
122.195
119.713
18.0913
22.1951
124.643
112.786
122.569
106.013
124.643
112.786
122.569
106.013

120.042
121.956
118.000
119.949
119.794
120.256
119.949
120.256
119.794
120.042
121.956
118.000
120.008
118.929
121.061
120.008
118.929
121.061
124.761
113.140
122.097
106.761
124.761
113.140
122.097
106.761

119.991
122.032
117.976
119.974
119.763
120.261
119.974
120.261
119.763
119.991
122.032
117.976
120.034
118.925
121.040
120.034
118.925
121.040
124.809
112.929
122.261
106.884
124.809
112.929
122.261
106.884

120.133
121.967
117.898
119.902
119.775
120.321
119.902
120.321
119.775
120.133
121.967
117.898
119.963
118.847
121.188
119.963
118.847
121.188
124.644
113.110
122.245
106.516
124.644
113.110
122.245
106.516

120.089
122.043
117.866
119.925
119.740
120.334
119.925
120.334
119.740
120.089
122.043
117.866
119.985
118.831
121.183
119.985
118.831
121.183
124.680
112.931
122.387
106.602
124.680
112.931
122.387
106.602

Dihedral angles ()
(C6C1C2C3)
(C6C1C2H7)
(C11C1C2C3)
(C11C1C2H7)
(C2C1C6C5)
(C2C1C6H10)
(C11C1C6C5)
(C11C1C6H10)
(C2C1C11O12)
(C2C1C11O13)
(C6C1C11O12)
(C6C1C11O13)
(C1C2C3C4)
(C1C2C3H8)
(H7C2C3C4)
(H7C2C3H8)
(C2C3C4C5)
(C2C3C4C15)
(H8C3C4C5)
(H8C3C4C15)
(C3C4C5C6)
(C3C4C5H9)
(C15C4C5C6)

0.0001
180.0004
180.0001
0.0004
0.0
179.9999
180.0
0.0001
180.0043
0.004
0.0043
180.004
0.0002
180.0003
180.0003
0.0008
0.0001
180.0001
180.0004
0.0004
0.0
179.9999
180.0

0.0032
179.9991
179.9999
0.004
0.0003
180.0008
180.0026
0.0022
179.9931
0.0019
0.0099
180.0049
0.0046
180.0004
180.0004
0.0039
0.0032
179.9999
179.9991
0.004
0.0003
180.0008
180.0026

0.0002
180.0
179.9998
0.0004
0.0001
179.9999
179.9997
0.0003
179.9991
0.0007
0.0005
179.9996
0.0002
180.0
180.0
0.0001
0.0002
179.9998
180.0
0.0004
0.0001
179.9999
179.9997

0.0017
180.0002
179.9992
0.0027
0.0005
179.9995
179.9981
0.0019
179.9958
0.0026
0.0067
179.995
0.0024
179.9996
179.9996
0.0015
0.0017
179.9992
180.0002
0.0027
0.0005
179.9995
179.9981

0.0002
180.0001
180.0
0.0004
0.0001
180.0001
179.9999
0.0002
180.0011
0.0013
0.0013
180.0015
0.0003
179.9999
179.9999
0.0004
0.0002
180.0
180.0001
0.0004
0.0001
179.9999
179.9999

0.0021
180.0003
179.9994
0.003
0.0006
179.9993
179.9979
0.0019
179.9988
0.0008
0.0039
179.9981
0.0028
179.9995
179.9995
0.0019
0.0021
179.9994
180.0003
0.003
0.0006
179.9993
179.9979

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N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242
Table 1 (continued)
Geometrical parameters

Computational methods
LSDA

(C15C4C5H9)
(C3C4C15O16)
(C3C4C15O17)
(C5C4C15O16)
(C5C4C15O17)
(C4C5C6C1)
(C4C5C6H10)
(H9C5C6C1)
(H9C5C6H10)
(C1C11O13H14)
(O12C11O13H14)
(C4C15O17H18)
(O16C15O17H18)

B3LYP

B3PW91

6-31++G(d,p)

6-311++G(d,p)

6-31++G(d,p)

6-311++G(d,p)

6-31++G(d,p)

6-311++G(d,p)

0.0001
180.0043
0.004
0.0043
180.004
0.0
180.0002
180.0002
0.0003
180.0029
0.0025
180.0029
0.0025

0.0022
179.9931
0.0019
0.0099
180.0049
0.0011
179.9993
179.9993
0.0002
180.0055
0.0005
180.0055
0.0005

0.0003
179.9991
0.0007
0.0005
179.9996
0.0
180.0
180.0
0.0
180.0032
0.003
180.0032
0.003

0.0019
179.9958
0.0026
0.0067
179.995
0.0001
180.0001
180.0001
0.0001
179.9942
0.0042
179.9942
0.0042

0.0002
180.0011
0.0013
0.0013
180.0015
0.0001
180.0
180.0
0.0001
180.0003
0.0005
180.0003
0.0005

0.0019
179.9988
0.0008
0.0039
179.9981
0.0002
180.0001
180.0001
0.0001
179.9981
0.0
179.9981
0.0

Table 2
Observed and calculated vibrational frequencies of terephthalic acid with DFT (B3LYP and B3PW91) method at 6-31++G(d,p) and 6-311++G(d,p) basis set.
S. No.

Symmetry species C2V

Observed frequency (cm1)

Computational methods
B3LYP

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

A1
A1
A1
A1
A1
A1
A1
A1
A1
A1
A1
B2
B2
A1
A1
A1
A1
A1
B2
B2
B2
B2
B2
B2
B1
B1
A2
A2
A2
A2
B2
B2
A1
A1
A1
B2
B2
A2
A2
A2
B2
B2
B1
B1
B1
B1
B1
B1

Vibrational assignments
B3PW91

FTIR

FT-Raman

6-31++G(d,p)

6-311++G(d,p)

6-311++G(d,p)

6-311++G(d,p)

3450w
3445w
3100w

3060w
1690vs
1680vs

1580m
1510s
1430vs
1410s
1300vs
1295vs
1290vs
1280vs

1140s

1020m
990w
970w
940s
930s
880s

780vs
775vs
730vs
725vs
685w

560m
530s
500w
450w

320w
310w
240w
230w
220w
150w

3095vs
3085m

1630vs
1620vs
1580w

1430w
1410vw
1300m

1290m

1185s

1125s

835vs
820w
805w

675vw
630vs

360w

3446
3445
3089
3083
3077
3071
1715
1712
1628
1615
1603
1501
1433
1421
1301
1272
1265
1245
1191
1136
1118
1010
988
967
955
915
885
833
823
791
760
799
734
730
694
670
610
549
538
512
474
331
285
272
170
90
87
59

3450
3449
3095
3087
3082
3076
1724
1720
1652
1608
1596
1493
1423
1414
1296
1279
1264
1246
1189
1133
1110
1046
989
970
957
936
867
832
814
793
762
807
743
742
679
657
616
557
543
513
483
335
290
267
173
87
84
59

3448
3447
3098
3092
3086
3048
1717
1714
1624
1631
1607
1504
1452
1438
1303
1284
1267
1248
1191
1137
1130
1013
987
967
954
932
868
822
810
793
763
808
736
736
705
681
615
555
544
513
476
334
283
275
169
90
87
60

3448
3447
3097
3088
3084
3076
1740
1738
1600
1625
1600
1498
1439
1427
1296
1281
1267
1249
1188
1133
1123
1007
994
974
960
937
867
821
818
796
766
811
742
737
684
662
616
558
545
511
481
335
285
268
170
87
85
60

(OH)t
(OH)t
(CH)t
(CH)t
(CH)t
(CH)t
(C@O)t
(C@O)t
(C@C)t
(C@C)t
(C@C)t
(OH)d
(OH)d
(CC)t
(CC)t
(CC)t
(CC)t
(CC)t
(CH)d
(CH)d
(CH)d
(CH)d
(CO)t
(CO)t
(OH)c
(OH)c
(CH)c
(CH)c
(CH)c
(CH)c
(C@O)d
(C@O)d
(CCC)d
(CCC)d
(CCC)d
(CC)d
(CC)d
(CCC)c
(CCC)c
(CCC)c
(CO)d
(CO)d
(CC)c
(CC)c
(CO)c
(CO)c
(COOH)s
(COOH)s

vs very strong; s strong; m medium; w weak; as asymmetric; s symmetric; t stretching; a deformation, d in plane bending; c out plane bending; s
twisting.

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N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

Table 3
Calculated unscaled frequencies of terephthalic acid by DFT (B3LYP and B3PW91) with 6-31+G(d,p) and 6-311++G(d,p) basis sets.
S. No.

Observed frequency

Calculated frequency
B3LYP

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

3450
3445
3100
3095
3085
3060
1690
1680
1630
1620
1580
1510
1430
1410
1300
1295
1290
1280
1185
1140
1125
1020
990
970
940
930
880
835
820
805
780
775
730
725
685
675
630
560
530
500
450
360
320
310
240
230
220
150

B3PW91

6-311++G (d,p)

6-31++G(d,p)

6-311++G(d,p)

6-31++G(d,p)

3766
3765
3235
3228
3222
3216
1796
1793
1661
1615
1541
1443
1378
1366
1362
1332
1216
1197
1191
1136
1118
1103
1035
1013
1000
897
868
817
807
746
717
701
644
640
609
588
535
482
472
449
416
290
250
239
149
79
76
52

3770
3769
3217
3209
3204
3197
1792
1788
1652
1608
1535
1436
1368
1360
1347
1330
1215
1198
1189
1133
1110
1095
1036
1016
1002
900
867
816
814
748
719
702
646
645
590
571
536
484
472
446
420
291
252
232
150
76
73
51

3797
3796
3244
3238
3231
3225
1817
1814
1674
1631
1545
1446
1396
1383
1379
1324
1218
1200
1191
1137
1130
1116
1034
1013
999
896
868
822
810
748
720
703
640
640
613
592
535
483
473
446
414
290
246
239
147
78
76
52

3797
3796
3226
3217
3212
3204
1813
1810
1667
1625
1538
1440
1384
1372
1371
1321
1218
1201
1188
1133
1123
1109
1035
1015
1000
901
867
821
818
751
723
705
645
641
595
576
536
485
474
444
418
291
248
233
148
76
74
52

CC vibrations
The ring C@C and CC stretching vibrations, known as semicircle stretching of hexagonal structure usually observed in the region
14001625 cm1 [2123]. The C@C stretching vibrations of the
present compound are strongly observed at 1630, 1620 and
1580 cm1. These assignments are in line with the literature
[24,25]. The CC stretching vibrations were observed at 1410,
1300 and 1295 cm1. When compared to the literature range cited
above, there is a considerable fall in the allowed range of observed
frequencies which is due to the increase of mass of substitutions
detained with the ring. Most of the C@C stretching bands are
observed with very strong intensity in IR and Raman. In the present
compound, three bands present at 730, 725 and 685 cm1 are
assigned to CCC in-plane bending and three supplementary bands
were at 560, 530 and 500 cm1 assigned to CCC out of plane bending. These assignments are in line with the assignments proposed
by the literature [26].

COOH group vibrations

The carbonyl group is most important in the infrared spectrum
because of its strong intensity of absorption and high sensitivity
toward relatively minor changes in its environment. Intra- and
inter-molecular factors affect the carbonyl absorptions in common organic compounds due to inductive, mesomeric effects,
eld effects and conjugation effects. The C@O stretching bands
of acids are considerably more intense than the ketonic C@O
stretching bands. The present compound posses couple of carboxyl group and usually, the C@O stretching vibrations observed
in the region 16001560 cm1. Dicarboxylic acids have two
strong bands due to C@O stretching vibration of the carboxyl
group at 16751750 cm1 [27,28] and another strong band at
12301140 cm1 due to the stretching of the CO bond [29,30].
The position of the band due to the CO stretching vibration is
dependent on the nature of both the acidic and the alcoholic
components.

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N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242
Table 4
The spectral data of 1H and

13

C NMR and the chemical shifts (ppm) of terephthalic acid.

Atom
position

B3LYP/6311+G(d,p)
(ppm)
Gas

TMS B3LYP/6311+G(2d,p) GIAO

(ppm)

Shift
(ppm)

B3LYP/6311+G(d,p)
(ppm)
DMSO

TMS B3LYP/6311+G(2d,p) GIAO

(ppm)

Shift
(ppm)

B3LYP/6311+G(d,p)
(ppm)
Chloroform

TMS B3LYP/6311+G (2d,p) GIAO

(ppm)

Shift
(ppm)

Experimental
values

C1
C2
C3
C4
C5
C6
C11
C15
H7
H8
H9
H10
H14
H18

40.22
46.81
46.81
40.22
45.71
45.71
8.98
8.98
23.79
23.79
23.51
23.51
26.17
26.17

142.24
135.65
135.65
142.24
136.75
136.75
191.45
191.45
8.08
8.08
8.36
8.36
5.70
5.70

102.02
88.84
88.84
102.02
91.04
91.04
182.47
182.47
15.71
15.71
15.15
15.15
20.47
20.47

39.88
45.56
45.56
39.88
45.93
45.93
11.45
11.45
23.62
23.62
23.50
23.50
25.49
25.49

142.58
136.89
136.89
142.58
136.52
136.52
193.91
193.91
8.25
8.25
8.37
8.37
6.38
6.38

102.7
91.33
91.33
102.7
90.59
90.59
182.46
182.46
15.37
15.37
15.13
15.13
19.11
19.11

39.98
45.95
45.95
39.98
45.80
45.80
10.77
10.77
23.67
23.67
23.50
23.50
25.67
25.67

142.47
136.50
136.50
142.47
136.65
136.65
193.23
193.23
8.20
8.20
8.38
8.38
6.20
6.20

102.49
90.55
90.55
102.49
90.85
90.85
182.46
182.46
15.47
15.47
15.12
15.12
19.47
19.47

130.0
120.0
120.0
130.0
120.0
120.0
170.0
170.0
9.15
9.15
9.15
9.15
9.0
9.0

Fig. 4. HOMO and LUMO view of terephthalic acid.

According to the literature, the very strong signals are appeared

at 1690 and 1680 cm1 for C@O stretching vibrations. It is found at
the top end of the C@O stretching region of the spectrum due to
the strong force constant (18.97 mdyne) of the bond. The other
two bands are with very strong to medium intensity identied at
990 and 970 cm1 for CO stretching vibrations. If the bond
lengths are different, the corresponding force constants are also
different. Though two CO bonds having same bond length
(1.356 ), the related two spikes are found sub sequentially with
20 cm1 intervals. These peaks also elevated down from the

expected region due to the due to the interaction of H of the ring.

The in plane and out of plane bending bands are found at 450 and
360 cm1 and 240 and 230 cm1, respectively. The entire bending
vibrations are suppressed much due to the interaction with ring.
Usually, the acid derivatives would have hydroxyl stretching
vibrations in the region of 34002500 cm1 [31,32]. The OH
group vibrations are likely to be the most sensitive to the surroundings, so they show pronounced shifts in the spectra of the
hydrogen bonded species. The band due to the OH stretching is
of medium to strong intensity in the infrared spectrum, although

236

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

it may be broad. The strong band appeared at 3450 and 3445 cm1
in the IR spectra are assigned to OH stretching mode of vibration.
The OH in-plane bending vibrations are observed in the region
14401260 cm1 [33] and the OH out of plane deformation vibration for phenol lays in the region 290320 cm1 for free OH and in
the region 517710 cm1 for associated OH [34]. In both interand intra-molecular associations, the wavenumber is at higher
value than that in the free OH. The wavenumber increases with
hydrogen bond strength because of large amount of energy
required to twist the OH bond [35]. The observed values of in
plane and out of plane bending vibrations of hydroxyl group are
1510 and 1430 and 940 and 930 cm1, respectively. The carbonyl
group is most important in the infrared spectrum because of its
strong dipole moment nature of absorption. Intra- and intermolecular factors affect the carbonyl absorptions in common
organic compounds due to inductive, mesomeric effects, eld
effects and conjugation effects. The COOH twisting vibrations are
found at 220 and 150 cm1 in the tail of the IR spectrum.

In the case of TA, the observed chemical shift of C1 and C4 are

130.0 ppm, respectively and C2, C3, C5 and C6 are 120.0 ppm,
respectively whereas the calculated shift of C1 and C4 are
102.7 ppm and C2, C3, C5 and C6 are 91.33, 91.33, 90.59 and
90.59 ppm, respectively. There is small difference between
observed and calculated values since the solvent nature. The chemical shift of C1 and C4 is more on the place of substitution than
other in the ring. This is mainly due to the breaking of paramagnetic shield of C by the diffusion of the carboxylic acid groups.
The chemical shift of C11 and C15 are 170.0 ppm which is more
shifted by the symmetrical occurrence of carbonyl and hydroxyl
groups on C. The shift of the entire carbons of the ring is found
nearly equal when compared with solvent phases. The chemical
shift of entire carbons in the molecule is abruptly changed. This
effect of addition of the COOH groups in the benzene ring is the
main cause to detain the present compound being acid.

NMR assessment

The frontier molecular orbitals (FMO) are very much useful for
studying the electric and optical properties of the concern organic
molecules. The stabilization of the bonding molecular orbital and
destabilization of the antibonding can be made by the overlapping
of molecular orbitals. The stabilization of the bonding molecular
orbital and destabilization of the antibonding can increase when
the overlap of two orbitals increases [38].
Normally, the molecular interactions take place between two
important sets of orbitals. One is the highest energy occupied
molecular orbital is called HOMO represents the ability to donate
an electron. The other one is the lowest energy unoccupied molecular orbital is called LUMO as an electron acceptor. These HOMO
LUMO patterns of orbitals are also called the frontier molecular
orbitals. The interaction between them is much stable and is called
lled empty interaction. When the two same sign orbitals overlap
to form a molecular orbital, the electron density will occupy at the
region between two nuclei. The molecular orbital resulting from

NMR spectroscopic tool is a breakthrough on organic structure

elucidation of much complicated complex molecules. The combined use of experimental and Gaussian computational tools offers
a powerful gadget to interpret and ensure the structure of bulky
molecules. The optimized structure of TA is used to calculate the
NMR spectra at B3LYP method with 6-311++G(d,p) level using
the GIAO method and the chemical shifts of the compound are
reported in ppm relative to TMS for 1H and 13C NMR spectra which
are presented in Table 4. The corresponding recorded and simulated spectra are shown in Fig. 7.
Normally, the range of 13C NMR chemical shifts for aromatic
ring is greater than 100 ppm [36,37] and the accuracy ensure that
the consistent interpretation of spectroscopic parameters. In the
present work, 13C NMR chemical shift of entire carbons in and
out of the ring is greater than 100 ppm, as in the expected regions.

Electronic characterization (frontier molecular analysis)

Fig. 5. Successive HOMO and LIMO diagrams for terephthalic acid.

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

237

Table 5
Electronic absorption spectra of terephthalic acid (absorption wavelength k (nm), excitation energies E (eV) and oscillator strengths (f) using TD-DFT/B3LYP/6-311++G(d,p)
method.
k (nm)

E (eV)

(f)

Major contribution

Assignment

Region

Bands

Gas
303.65
300.72
286.50
256.60
213.71

4.082
4.1230
4.3275
4.8318
5.8015

0.0001
0.000
0.0289
0.4615
0.0218

H ? L (92%)
H ? L (89%)
H ? L  1 (86%)
H + 1 ? L (86%)
H ? L  1 (78%)

n ? p
n ? p
n ? p
n ? p
p ? p

Quartz UV

R-band (German, radikalartig)

DMSO
294.78
291.63
263.54
212.93
212.49

4.2061
4.2515
4.7045
5.8226
5.8347

0.004
0.0003
0.5795
0.0324
0.0368

H ? L (90%)
H ? L  1 (90%)
H ? L  1 (87%)
H + 1 ? L  1 (83%)
H + 1 ? L  1 (75%)

n ? p
n ? p
n ? p
n ? p
p ? p

Quartz UV

R-band (German, radikalartig)

Chloroform
294.20
292.59
263.19
212.94
211.97

4.2143
4.2374
4.7108
5.8226
5.8490

0.0001
0.0429
0.5840
0.0356
0.000

H ? L (86%)
H ? L  1 (85%)
H + 1 ? L (78%)
H + 1 ? L  1(77%)
H + 1 ? L  1 (75%)

n ? p
n ? p
n ? p
n ? p
p ? p

Quartz UV

R-band (German, radikalartig)

CCl4
296.70
291.01
262.73
213.40
212.26

4.1788
4.2605
4.7190
5.8100
5.8412

0.00
0.0430
0.5851
0.0340
0.00

H ? L (86%)
H ? L  1 (85%)
H + 1 ? L (78%)
H + 1 ? L  1(74%)
H + 1 ? L  1 (75%)

n ? p
n ? p
n ? p
n ? p
p ? p

Quartz UV

R-band (German, radikalartig)

H: HOMO; L: LUMO.

Table 6
Calculated energies, chemical hardness, electro negativity, chemical potential,
Electrophilicity index of terephthalic acid in UVVisible region.
TD-DFT/B3LYP/6-311G++(d,p)

Gas

DMSO

Ethanol

Methanol

Etotal (Hartree)
EHOMO (eV)
ELUMO (eV)
DEHOMOLUMO gap (eV)
EHOMO1 (eV)
ELUMO+1 (eV)
DEHOMO1LUMO+1 gap (eV)
Chemical hardness (g)
Electronegativity (v)
Chemical potential (l)
Chemical softness (S)
Electrophilicity index (x)
Dipole moment

609.54
9.6695
4.5443
5.1252
9.7201
5.4373
4.2828
2.5626
7.1069
2.5626
0.1951
9.8548
2.5704

609.56
9.6695
5.373
4.2322
9.7201
4.5443
5.1758
2.1161
7.5534
2.1161
0.2362
13.480
3.1494

609.55
9.6745
5.4373
4.2372
9.7201
4.5443
5.1758
2.1186
7.5559
2.1186
0.2360
13.473
3.1494

609.55
9.6695
5.4373
4.2322
9.7201
4.5443
5.1758
2.1161
7.5534
2.1161
0.2362
13.480
2.9222

in-phase interaction is dened as the bonding orbital which contain energy lower than the original atomic orbital. The out of phase
interaction forms the anti bonding molecular orbital with energy
higher than the initial atomic orbital.
The 3D plots of the frontier orbitals, HOMO and LUMO for TA
molecule are in gas, shown in Figs. 4 and 5. According to Fig. 4,
the HOMO is mainly localized by two Pi bond orbital lobes over
the benzene ring and two sigma bond interaction taking place over
@O and AO of COOH group. The antibonding orbital lobes are also
taking place over some part of the molecule. However, LUMO is
characterized by a charge distribution connects the entire carbon
atoms of the ring and COOH group atoms in which there are four
Pi bond interaction taking place over the pair of carbon bonds in
opposite sides of the ring and ring carbon and Carboxyl group carbons. In addition to that, some sigma bond interaction taking place
over C of COOH. From this observation, it is clear that, the strong
sigma bond interaction found at carbonyl group and Pi bond interaction found between C of ring and carboxyl groups. Apart from
that, the in and out of phase interaction are present in HOMO

and LUMO, respectively. The HOMO ? LUMO transition implies

an electron density distributed among the C of ring and COOH
groups. Thus the inter charge transformation occur between base
and substitutions. The energy relationship between HOMO and
LUMO is presented in Table 7 and the diagram is displayed in
Fig. 8. As per the table, HOMO and LUMO energy are 9.817 and
5.459 eV in gas phase (Fig. 4). The energy difference between
HOMO and LUMO orbital is called as energy gap (kubo gap) that
is an important stability for structures. The DFT level calculated
energy gap is 4.357 eV which shows the medium energy gap and
reect the moderate electrical activity of the molecule.

Optical characterization (HOMOLUMO analysis)

The UV and visible spectroscopy is used to detect the presence
of chromophores in the molecule and whether the compound has
NLO properties or not. The calculations of the electronic structure
of TA are optimized in singlet state. The low energy electronic
excited states of the molecule are calculated at the B3LYP/6311++G(d,p) level using the TD-DFT approach on the previously
optimized ground-state geometry of the molecule. The calculations
are performed in gas phase and with the solvent of DMSO, chloroform and CCl4. The calculated excitation energies, oscillator
strength (f) and wavelength (k) and spectral assignments are given
in Table 5. The major contributions of the transitions are designated with the aid of SWizard program [39].
TD-DFT calculations predict that, irrespective of the gas and solvent phase, the entire transitions belong to quartz ultraviolet
region. In the case of gas phase, the strong transitions are at
286.50, 256.60 and 209.21 nm with an oscillator strength
f = 0.028, 0.461 and 0.021 with excitation energy of 4.32, 4.83
and 5.80 eV. The possible transitions are n ? p and p ? p in
quartz ultraviolet region. The whole transitions represented by Rband (German, radikalartig) which is due to the addition of chromophoric group; COOH. They are characterized by low molar
absorptivities (nmax < 100) and undergo hypsochromic to bathochromic shift and the solvent effect is inactive in this compound.

238

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

Fig. 6. Molecular electrostatic potential and contour of terephthalic acid.

Table 7
Frontier molecular orbitals with energy levels.
Energy levels

Energy in eV

H+8
H+7
H+6
H+5
H+4
H+3
H+2
H+1
H
L
L1
L2
L3
L4
L5
L6
L7
L8
L9
L  10

12.338
12.292
12.149
10.521
10.505
9.986
9.955
9.926
9.817
5.459
4.480
3.060
1.152
0.089
0.489
0.665
1.029
1.066
1.893
2.442

In the case of DMSO solvent, strong transitions take place at

274.02, 264.47, 244.44 and 241.64 nm with an oscillator strength
f = 0.03, 0.02, 0.005 and 0.003 with maximum energy gap
5.13 eV. Such excitation assigned to n ? p transition and it
belongs to quartz ultraviolet region. The result of the UV bands
shows that, from gas state to solvent phase, the electronic transitions would not be shifted from quartz ultraviolet region. This view
indicates that, the TA molecule is UV active and it is capable of having rich biological properties. In addition to that, the calculated
optical band gap 3.57 eV which is also ensure that, the present
compound possessing biological as well as NLO properties. In view
of calculated absorption spectra, the maximum absorption wavelength corresponds to the electronic transition from the HOMO + 1
to LUMO  1 with maximum contribution. In this present

Table 8
The dipole moments l (D), the polarizability a (a.u.), the average polarizability a0
(esu), the anisotropy of the polarizability Da (esu), and the rst hyperpolarizability b
(esu) of the compound; a-methylstyrene.
Parameter

a.u.

Parameter

a.u.

axx
axy
ayy
axz
ayz
azz
atotal
Da
lx
ly
lz
l

69.79
0.0001
3.244
0.00
0.00
1.3386
55.71
84.36
0.00
0.00
2.7331
2.7331

bxxx
bxxy
bxyy
byyy
bxxz
bxyz
byyz
bxzz
byzz
bzzz
btotal

0.00
0.00
0.00
0.00
0.0227
0.0014
71.6318
0.00
0.00
3.0008
13.87

Table 9
Specic heat capacity, entropy and enthalpy at different temperatures for terephthalic
acid.
T (K)

C0p,m (cal mol1 K1)

S0m (cal mol1 K1)

DH0m (cal mol1 K1)

100
200
298.15
300
400
500
600
700
800
900
1000

323.84
430.46
530.85
532.73
632.58
727.91
817.44
900.89
978.54
1050.85
1118.37

115.23
206.13
302.47
304.22
391.60
462.72
518.88
563.36
599.15
628.47
652.85

7.24
23.14
48.14
48.70
83.62
126.47
175.66
229.86
288.04
349.47
413.57

compound, the chromophore is COOH group where the conjugated

double bonds (C@O) causes the absorption band at quartz UV
region. In addition to that, due to the COOH the acetic property
is enhanced in the present compound.

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Fig. 7. Experimental and simulated 1H and

Chemical parameters analysis

The chemical hardness, chemical potential, electronegativity
and Electrophilicity index of the title compound are calculated
and their values are presented in Table 6. The chemical hardness
of the present molecule is nearly equal (2.112.56) in going from
Gas to solvent phase. Therefore, the high value of chemical hardness of present compound has exposed its tough chemical stability.
The substitution of pair of COOH group enhanced the chemical stability and acid character of the compound. Similarly, the electronegativity of this case is increased from 7.10 up to 7.55, from
Gas to solvent, whenever the value is greater than 1.7; the character of chemical bond character is changed from covalent to ionic.
Accordingly, by the addition of COOH group, the bonds character
of the compound rehabilitated to ionic.
The Electrophilicity index is a factor which is a measure of
energy lowering due to maximal electron ow between donor
[HOMO] and acceptor [LUMO]. From the Table 6, it is found that
the Electrophilicity index is 9.85 in gas and 13.48 in solvent, which
is so high and ensures that the strong energy transformation is taking place as a excitation between HOMO + 1 and LUMO  1 instead
of HOMOLUMO.
The dipole moment of a molecule is another important electronic property and it explores the electronic energy distribution
in a compound. The large dipole moment of the molecule always
ensures that the very strong intermolecular interaction. The calculated dipole moment of the title compound is 2.57 Debye in gas
and 3.14 in solvent. It is normally high which is also inferred that,
the present molecule has strong intermolecular interactions.

Molecular electrostatic potential (MEP) maps

The molecular electrical potential surfaces illustrate the three
dimensional charge distributions of molecule. This map visualizes
the negative and positive charged region of the molecule. Facts of

239

13

C NMR spectra of terephthalic acid.

the charge distributions are much useful to determine how molecules interact with other compounds to be associated and it is also
used to determine the requirement of minimum energy to connect
with other structure [40]. Molecular electrostatic potential view is
mapped up at the level of B3LYP/6-311+G(d,p) theory with optimized geometry. There is a great deal of intermediary potential
energy, the non red or blue region indicates that the electro negativity difference is not very great. In a molecule with a great electro
negativity difference, charge is very polarized in negative and positive form, and there are signicant differences in electron density
in different regions of the molecule. This great electro negativity
difference leads to regions that are almost entirely red and almost
entirely blue. The region of intermediary potential is explored by
green and yellow color and the regions of extreme potential looks
like red and blue colors are key indicators of electronegativity.
The color codes of this map are in the range between
4.211 a.u. (deepest red) to 4.211 a.u. (deepest blue) in compound.
The positive (blue1) region of MEP is related to electrophilic reactivity and the negative (green) regions to nucleophilic reactivity shown
in Fig. 6. From the MEP map of the title molecule, it can be seen
clearly that, the negative region is mainly localized on C@O of COOH
group. A maximum positive region is localized around OH which
indicating a possible site of nucleophilic attack. Though, the molecule contains two COOH group with benzene ring, the positive and
negative potential regions located at the COOH group. From these
results, it is inferred that, when the compound docked with protein
structure, the reaction path is to be via COOH group in the molecule.

Polarizability and First order hyperpolarizability calculations

In order to investigate the relationships among the molecular
structures, non-linear optic properties (NLO) and molecular bind1
For interpretation of color in Fig. 6, the reader is referred to the web version of
this article.

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Fig. 8. Energy levels of frontier molecular orbitals.

ing properties, the polarizabilities and rst order hyperpolarizabilities of the present compound are calculated using DFT-B3LYP
method and 6-311+G(d,p) basis set, based on the nite-eld
approach. The Polarizability and hyperpolarizability tensors are
obtained from the output le of Polarizability and hyperpolarizability calculations. However, a and b values of Gaussian output
are in atomic units (a.u.) have been converted into electronic units
(esu) (a; 1 a.u. = 0.1482  1024 esu, b; 1 a.u. = 8.6393  1033 esu). The mean polarizability (a), anisotropy of polarizability
(Da) and the average value of the rst hyperpolarizability hbi can
be calculated.
In Table 8, the calculated parameters described above and electronic dipole moment {li(i = x, y, z) and total dipole moment ltotal}
for title compound are listed. It is well known that, molecule with
high values of dipole moment, molecular Polarizability, and rst
hyperpolarizability possesses more active NLO properties. The rst
hyperpolarizability (b) and the component of hyperpolarizability
bx, by and bz of TA along with related properties (l0, atotal, and
Da) are reported in Table 8. The calculated value of dipole moment
is found to be 2.733 Debye. The highest value of dipole moment is
observed in the component of lZ which is 2.733 D since the
dipole vector is oriented negative Z direction. The dipole moment
is zero in lX and lY component. The calculated average Polarizability and anisotropy of the Polarizability is 55.71  1024 esu and
84.36  1024 esu, respectively. The magnitude of the molecular
hyperpolarizability b, is one of important key factors in a NLO system. The B3LYP/6-311+G(d,p) calculated rst hyperpolarizability
value (b) is 13.87  1030 esu. From the above results, it is
observed that, the molecular Polarizability and hyperpolarizability
of the title compound in two perpendicular coordinates (yyz) are
active. So that, whenever the present compound is energized, the
second order harmonic waves with more amplitude is generated.
Apart from that, due to the elevated values of Polarizability and
hyperpolarizability, the present compound is able to bind with
other molecules with less amount of binding energy.
Thermodynamic properties
Normally, the thermo dynamical analysis on aromatic compound is very important since they provide the necessary information regarding the chemical reactivity. On the basis of vibrational
analysis at B3LYP/6-311G(d,p) level the standard statistical thermodynamic functions: standard heat capacities (C0p,m) standard
entropies (S0m), and standard enthalpy changes (DH0m) for the title
compounds were obtained from the theoretical harmonic

Fig. 9. Thermodynamic parameters at different temperatures.

frequencies and listed in Table 9. From Table 9, it can be observed

that these thermodynamic functions are increasing with temperature ranging from 100 to 1000 K due to the fact that the molecular
vibrational intensities increase with temperature [41,42]. The correlation graph between heat capacities, entropies, enthalpy
changes and temperatures were shown in Fig. 9. At lower and
higher temperature, the specic heat capacity of the present compound obeys the Debye T3 law. The value entropy and enthalpy of
the terephthalic acid gets elevated and saturated at 1000K.
Mass spectral analysis
Generally the mass spectroscopic tool is used for identifying the
molecular formula by cleavage fragmentation. The molecule fragmentation view and the recorded mass spectrum of the present
compound are shown in Figs. 10 and 11 respectively. Highly

N. Karthikeyan et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 139 (2015) 229242

241

Fig. 10. Mass spectra-molecular fragmentation of terephthalic acid.

Fig. 11. Mass spectrum of terephthalic acid.

branched substances undergo fragmentation very easily. The separations of molecular ions with respect to their mass of the base and
substitution of the terephthalic acid are observed as peaks in the
spectrum. The observed abundance of the suspected molecular
ion must be corresponding to expectations based on the assumed
molecule structure. The possible fragmentation is as shown in
Fig. 11 according to the observed peaks in spectrum. The formula
for present compound is deduced from the molecular mass separation with appropriate mass. Thus, the molecular structure is
approved by the mass separation.
Conclusion
In the present research work, the title compound was thoroughly investigated using FT-IR, FT-Raman, NMR and mass spectral

data. The geometrical and vibrational parameters were calculated

using hybrid computational calculations; DFT (B3LYP and
B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis
sets. The molecular mass data related to base molecule and substitutional group of the compound was analyzed. The modication of
the chemical property by the reaction mechanism of the injection
of di-carboxylic group in the benzene ring was investigated. The
absolute chemical shifts related to TMS were compared with
experimental spectra. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment
and frontier molecular orbital energies, were performed using
sophisticated tool. The orbital energies for different levels of
HOMO and LUMO were calculated and the molecular orbital lobe
overlapping showed the inter charge transformation between the
base and ligand group. From the frontier molecular orbitals
(FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the compound related to Polarizability
and hyperpolarizability are also discussed. The mass fragmentation
data has been studied using mass spectrum.

Acknowledgement
The authors thank all the ofcials of academic and non academics of Anna University, BIT Campus, Tiruchirappalli, Tamilnadu,
India.

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