Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230

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Spectrochimica Acta Part A: Molecular and

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

Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation on 1-

phenyl-2-nitropropene by quantum computational calculations
S. Xavier a,b,, S. Periandy c
a
Department of Physics, St. Joseph College of Arts and Science, Cuddalore, Tamil Nadu, India
b
Bharathiyar University, Coimbatore, Tamil Nadu, India
c
Department of Physics, Tagore Arts College, Puducherry, India

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 compound 1-phenyl-2- 1-Phenyl-2-nitropropene is one of the important intermediate preparation of amphetamine, which is
nitropropene has been investigated widely used as cognitive enhancer drug of the central nervous system. It exhibits the property of the
using FT-IR, FT-Raman and NMR and dipole moment and hyperpolarizability three times higher than the NLO property of the urea. There
UVVis spectroscopic tool. are larger charge distribution and ow of charge from electrophile to nucleophile in the molecule.
 The chemical shift of the compounds
is found and it is favorable for its
change of chemical property.
 The charge transfer in the molecule
by HOMOLUMO is studied in
relation with NBO analysis.
 The study of NLO property in relation
with dipole moment and
hyperpolarizability is done.
 Chemical reactivity region has been
found along with the Fukui function.

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, the spectral analysis of 1-phenyl-2-nitropropene is carried out using the FTIR, FT Raman, FT
Received 8 December 2014 NMR and UVVis spectra of the compound with the help of quantum mechanical computations using ab-
Received in revised form 25 March 2015 initio and density functional theories. The FT-IR (4000400 cm1) and FT-Raman (4000100 cm1) spec-
Accepted 20 April 2015
tra were recorded in solid phase, the 1H and 13C NMR spectra were recorded in CDCl3 solution phase and
Available online 25 April 2015
the UVVis (200800 nm) spectrum was recorded in ethanol solution phase. The different conformers of
the compound and their minimum energies are studied using B3LYP functional with 6-311+G(d,p) basis
Keywords:
set and two stable conformers with lowest energy were identied and the same was used for further
1-Phenyl-2-nitropropene
Chemical shifts
computations. The computed wavenumbers from different methods are scaled so as to agree with the
NBO experimental values and the scaling factors are reported. All the modes of vibrations are assigned and
HOMOLUMO the structure the molecule is analyzed in terms of parameters like bond length, bond angle and dihedral
Fukui function angle predicted by both B3LYP and B3PW91 methods with 6-311+G(d,p) and 6-311++G(d,p) basis sets.
The values of dipole moment (l), polarizability (a) and hyperpolarizability (b) of the molecule are
reported, using which the non-linear property of the molecule is discussed. The HOMOLUMO mappings
are reported which reveals the different charge transfer possibilities within the molecule. The isotropic
chemical shifts predicted for 1H and 13C atoms using gauge invariant atomic orbital (GIAO) theory show
good agreement with experimental shifts. NBO analysis is carried out to picture the charge transfer

Corresponding author at: Department of Physics, St. Joseph College of Arts and
Science, Cuddalore, Tamil Nadu, India. Tel./fax: +91 9443428971.
E-mail address: puduvaixavier@gmail.com (S. Xavier).

http://dx.doi.org/10.1016/j.saa.2015.04.055
1386-1425/ 2015 Elsevier B.V. All rights reserved.
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 217

between the localized bonds and lone pairs. The local reactivity of the molecule has been studied using
the Fukui function. The thermodynamic properties (heat capacity, entropy and enthalpy) at different
temperatures are also calculated.
2015 Elsevier B.V. All rights reserved.

Introduction geometry is used for the conformational analysis using semi-

empirical method with PM6 basis set. The electronic properties,
1-Phenyl 2-nitropropene [1P2NP] is an aromatic hydrocarbon such as NBO and HOMOLUMO were calculated using time-depen-
with nitro and propene substitution in the phenyl ring. It is green- dent TD-SCF B3LYP method under the same basis set. Similarly
ish-yellow solid powder from which certain vital drugs are synthe- the NMR chemical shifts are also carried out by GIAO method in
sized. Amphetamine, one of the important derivative of 1P2NP, is a combination with B3LYP/6-311G+(2d, p). In addition, Fukui func-
prime central nervous system stimulant, and an important tion, the dipole moment, linear polarizability and the rst order
member of phenyl ethylamine drug family that are used in the hyper polarizability of the title molecule are also computed using
treatment of attention deciency, hyperactivity disorder and nar- B3LYP method with the 6-311+G(d,p) basis set.
colepsy. Amphetamine is also used as performance and cognitive
enhancer, and recreationally as aphrodisiac and euphoriant [1].
Results and discussion
The compound 1P2NP is also known as b-methyl-b-nitrostyrene
or trans-b-methyl-b-nitrostyrene.
Conformational analysis
Jack DeRuiter et al. have investigated the conversion of 1P2NP
to amphetamine under variety of reaction conditions using gas
The optimized geometry of the molecule obtained using B3LYP
chromatography and mass spectrometry [2]. The versatile interme-
with 6-311+G(d,p) basis set was used for conformational analysis
diate was prepared by treating benzaldehyde with butylamine and
of the molecule. Conformational analysis was performed by poten-
nitroethane. Reduction of the nitro propene with a 5-molar excess
tial energy surface scan function semi-empirical method with PM6
of lithium aluminum hydride was found to yield 1-phenyl-2-
basis set and by varying the torsion angle C18-C14-N15 in the
proponoxime and partial reduction with large excess of lithium
steps of 36 over one complete rotation 0360 as recommended
aluminium hydride yielded amphetamine. 1P2NP was also con-
in the previous work on a similar molecule [4]. The graphical
verted into ketone, 1 phenyl 2-propene, by partial reduction and
result, total energy verses scan coordinates, of this conformer anal-
hydrolysis. Amination of this ketone under Leuckart and reductive
ysis is presented in Fig. 1. The graph clearly shows that there are
amination conditions provided amphetamine as the principle
two conformers at minimum energy levels, one at 80 and the
product. GCMS analysis revealed that these samples also contain
other at 220 with total energy 0.1636 and 0.1637 hatree, respec-
several other by-products. However, literature survey indicates
tively. The structure of the molecules at these conformation is
that much works have not been carried out on these molecules,
shown in Fig. 1, as conformer I and II, of which the conformer I
particularly on 1P2NP. Hence a thorough and systematic spectral
represents the most stable conformer of this compound.
analysis is attempted on 1P2NP with the help standard experimen-
Praveen et al. [5,6] have made conformational analysis in the
tal and computational techniques.
case of p-tolytrichloro silane, which showed that the conformer
with staggered structure gives lowest energy conguration
Experimental details whereas the conformer with eclipsed structure gives highest
energy conguration. Exactly similar observation is also made in
The compound 1-phenyl-2-nitropropene was purchased in the this molecule, a staggered form of C18C14N15 gives a most
powder form from SigmaAldrich Chemicals, Chennai. The FT-IR stable conformation and an eclipsed form gives the highest unsta-
spectrum of the compound was recorded using a Bruker IFS 66V ble conformer of the molecule1P2NP.
spectrometer in the range of 4000400 cm1. The spectral resolu-
tion is 2 cm1. The FT-Raman spectrum of the same compound
was also recorded using the same instrument with an FRA 106
Raman module equipped with a Nd: YAG laser source operating
at 1.064 lm line widths with 200 mW power, in the range of
4000100 cm1 with a scanning speed of 30 cm1 min1and spec-
tral width 2 cm1. The frequencies of all bands are accurate to
1 cm1. The high resolution H NMR and C NMR spectra were
recorded using 300 MHz and 75 MHz NMR spectrometer, respec-
tively. The UVVis spectra was recorded in liquid phase dissolved
in ethanol in the range of 200800 nm, with the scanning interval
of 0.2 nm, using the UV-1700 series instrument.

Computational details

The entire quantum chemical computations are performed

using the Gaussian 09 software on a Pentium IV/3.02 GHz personal
computer [3]. The wave numbers and geometrical parameters are
computed using HF, B3LYP and B3PW91 methods in combination
with 6-311+G(d,p) and 6-311+G(d,p) basis sets. The geometry of
the title molecule 1-phenyl-2-nitropropene is fully optimized
using B3LYP functional with 6-311+G(d,p) basis set and the same Fig. 1. Potential energy surface of 1-phenyl-2-nitropropene.
218 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230
Molecular geometry
The stable conguration of the molecule obtained from the con-
former analysis which has been used for the structural analysis is
shown in Fig. 2. The calculated bond length, bond angle and
dihedral angle obtained using HF, B3LYP and B3PW91 methods
with 6-311+G(d,p) basis sets for this conguration with experi-
mental values are presented in Table 1. The comparative bar dia-
gram for bond lengths is presented in Fig. 3a. The CC bond
lengths of the aromatic ring varies between 1.38 and 1.39 in all
the methods, the experimental value also lie closer to these values,
which signies that the demarcation between single and double
bond is not possible within the ring due to the conjugation of the
electron. But in case of the propene substitution, the bond length
C12C14 clearly shows that it is double bond with value 1.32 in
HF and 1.342 in B3LYP and B3PW91 methods, while the experi-
mental value is 1.33 . The two CC bond lengths C3C12 and C14
C18 are longer (1.48 ) than any value inside the ring which shows
only these two bonds here are pure single bonded CC, which again
conrms the conjugation of the electrons inside the benzene ring.
In the case CH bond lengths, it is observed that all the CH bond
lengths whether in phenyl ring or in the methyl group, show
almost the same value 1.081.09 , agreeing with the experimen-
tal value which show that these bond lengths are not subjected to
any external inuence. Similarly in the nitro group, there are two
NO bond lengths, with computed values 1.188 in HF and
1.22 in B3LYP and B3PW91 methods, the experimental value is
1.22 which again shows that these bonds are remain uninu-
enced and the theoretical approximations are valid for these bonds.
The comparative bar diagram for bond angle is presented in
Fig. 3b. This diagram shows that the bond angle at every carbon
atom in the benzene ring is 120 in all the methods, which is
slightly higher than the experimental value 119.5. This fact indi-
cates that the hexagonal structure of the phenyl ring is remain
undisturbed in this molecule by the substitutional group.
Vibrational assignments
The vibrational frequencies for all the fundamental modes of
1-phenyl-2-nitropropene, are computed using HF, B3LYP,
B3PW91 methods with 6-311+G(d,p) basis sets and the values
along with the experimental values and assignments are presented
in Table 2. The molecule consists of 21 atoms and belongs to C1
point group, hence the 57 fundamental modes of vibrations are
distributed as Cvib = 39 A0 + 18 A00 . In order to t the theoretical
and experimental frequencies, suitable scaling factors are
introduced. The scaling factors are 0.914, and 0.9067 for HF/6-
311+G(d,p) and 0.9628 and 0.959 for B3LYP/6-311+G(d,p) and
B3PW91/6-311+G(d,p), respectively. The experimental and
Fig. 2. Molecular structure of 1-phenyl-2-nitropropene.
computational IR and Raman spectra of the compound are shown
in Figs. 4 and 5, respectively.
Aromatic CH vibrations
The CH stretching vibrations of the phenyl ring are normally
observed in the region 31003000 cm1 [1011] which shows
their uniqueness of the skeletal vibrations. In the present molecule
the stretching vibrations appear at 3090, 3080, 3070, 3060,
3010 cm1. All the ve bands are well within the expected range
which shows the aromatic nature of the phenyl ring is not dis-
turbed by any of the substitutional group. All these vibrations are
found active only in IR not in Raman.
Similarly, the CH in-plane ring bending vibrations for aromatic
CH occurs as strong to weak intensity bands in the region 1300
1200 cm1 [12]. In the present compound, the bands are observed
at 1350, 1330, 1320, 1300 and 1270 cm1. The last vibration
1270 cm1 is observed in FT-Raman with very strong intensity.
Except the one vibration, others are observed in the expected
region. The CH out-of-plane bending vibrations are expected in
the region 1000800 cm1 [13]. But these vibrations are found at
860, 760, 720, 700 and 680 cm1 in the present case. This shows
only the out-of-plane bending vibrations are inuenced by the
other modes, particularly the NO and CC in plane bending modes
which also falls in this range. This trend was also observed by
Badawiin 2-4 dichlorophenoxyacetic [14].
Propene group vibrations
The aliphatic CH stretching bands are expected between 3000
and 2900 cm1 [15]. In the present compound the vibrations of
the propene group are observed at 2990, 2980, 2970 and
2960 cm1. Similarly, the in-plane and out-of-plane deformation
of such CH bands are expected in the regions 12001100 cm1
and 900700 cm1. Four bands for each in-plane and out-of-plane
are observed at 1220, 1160, 1110 and 1090 cm-1 and 670, 660, 580
and 570 cm1, respectively. These observations indicate that the
stretching and in-plane bending are observed within the expected
region and out-of-plane vibrations are found below its expected
range. This trend is exactly same as that in benzene ring CH. This
shows that the CH vibrations both aromatic and aliphatic remain
independent of other vibrations in the molecule except the out of
plane bending vibrations where NO and CC in-plane bindings
interfere.
The CC vibrations
The CC stretching vibrations for phenyl ring are generally
observed between 1600 and 1400 cm1 [16], in which the bands
between 1600 and 1500 cm1 are assigned to C@C stretching and
the rest to CC stretching, even though no such distinction is pre-
sent within the ring. In the present compound also, the bands
observed at 1630, 1620, and 1580 cm1 are assigned to C@C and
the bands at 1480, 1460, 1440 to CC in the phenyl ring. These
observations for the aromatic CC are in agreement with literature
values, which indicate that the skeletal vibrations are not affected
by the substitutional vibrations.
In the case of propene group, there are two CC and one C@C
whose stretching vibrations are observed at 1680 cm1 for C@C
and at 1505 and 1490 cm1 for CC. The in-plane bending and out-
of-plane bending vibrations for C@C are assigned at 1090 and
670 cm1, respectively. The same thing for CC are assigned at 970
& 950 and 570 & 540 cm1, respectively. These observation also
are in agreement with the above cited literatures [17], except the
bands for out of plane bending of CC, which is again due to the inter-
ference of NO group, whose out of plane bending vibrations also lie
in this range. Hence, it may be concluded that the CC vibrations in
substitutional group are also not affected by the presence of other
vibrations in the molecule except the CC out of plane bending.
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 219

Table 1
The optimized geometrical parameters of 1-phenyl-2-nitropropene.

Geometrical parameter HF/6-311+G(d,p) B3LYP/6-311+G(d,p) B3PW91/6-311+G(d,p) Experimentala

C1C2 1.3831 1.3899 1.3878 1.3878a
C1C6 1.3860 1.3946 1.3924 1.3940a
C1H7 1.0751 1.0839 1.0849 1.0816a
C2C3 1.3927 1.4067 1.4039 1.3850a
C2H8 1.0759 1.0847 1.0857
C3C4 1.3908 1.4057 1.4028 1.3860a
C3C12 1.4801 1.4648 1.4612 1.501a
C4C5 1.3849 1.3912 1.3891 1.3910a
C4H9 1.0742 1.0820 1.0834
C5C6 1.3848 1.3944 1.3921 1.3890a
C5H10 1.0752 1.0841 1.0851
C6H11 1.0752 1.0840 1.0849
H9H20 2.4327 2.2194 2.2340
C12H13 1.0741 1.0851 1.0866 1.081b
C12@C14 1.3223 1.3424 1.3411 1.336b
C14N15 1.4794 1.4911 1.4843 1.501b
C14C18 1.4996 1.4943 1.4885
N15O16 1.1890 1.2261 1.2202 1.214b
N15O17 1.1880 1.2274 1.2216 1.218b
C18H19 1.0825 1.0904 1.0913
C18H20 1.0801 1.0893 1.0901 1.09b
C18C21 1.0842 1.0942 1.0946
C2C1C6 120.0405 120.0267 120.0334 119.96
C2C1H7 119.7868 119.8109 119.8066
C6C1H7 120.1707 120.1596 120.1572
C1C2C3 120.678 121.015 120.9384 119.35
C1C2H8 119.731 119.8081 119.8709
C3C2H8 119.5889 119.1738 119.1867
C2C3C4 118.8211 118.2253 118.3341
C2C3C12 118.3896 117.7923 117.9828
C4C3C12 122.7379 123.9469 123.6488
C3C4C5 120.4762 120.6374 120.6021
C3C4H9 120.0091 120.0563 119.9436
C5C4H9 119.4972 119.2626 119.4067
C4C5C6 120.237 120.3809 120.3493
C4C5H10 119.6503 119.6037 119.6231
C6C5H10 120.1116 120.0131 120.0251
C1C6C5 119.7188 119.6756 119.7006
C1C6H11 120.142 120.1831 120.1685
C5C6H11 120.1357 120.1349 120.1242
C4H9H20 92.5881 101.7619 99.6507
C3C12H13 115.9131 115.6874 116.1269 117b
C3C12C14 127.2196 128.8741 128.4185
H13C12C14 116.8571 115.4169 115.4306
C12C14N15 115.8654 115.6994 115.7076 119b
C12@C14C18 130.0168 129.9644 129.8443 124.3b
N15C14C18 114.1127 114.3226 114.4289
C14N15O16 119.4448 119.5818 119.4748
C14N15O17 116.2159 116.3358 116.2352
O16N15O17 124.3385 124.0808 124.2885
C14C18H19 110.2316 110.2884 110.2296
C14C18H20 109.4078 109.9179 109.8786 111b
C14C18H21 111.6486 111.917 111.9238 111b
H19C18H20 108.7679 108.9967 109.0506
H19C18H21 107.5173 106.8174 106.7831
H20C18H21 109.2055 108.8124 108.8877
H9H20C18 103.657 105.5368 104.984
C6C1C2C3 1.3436 1.457 1.4959
C6C1C2H8 179.1928 179.1941 179.2393
H7C1C2C3 179.1713 179.1499 179.1057
H7C1C2C8 0.2922 0.1991 0.1591
C2C1C6C5 0.1033 0.2786 0.3056
C2C1C6H11 179.4211 179.3664 179.3603
H7C1C6C5 179.3797 179.1124 179.0907
H7C1C6H11 0.0619 0.0246 0.0361
C1C2C3C4 2.0087 2.3204 2.4074
C1C2C3C12 179.4739 179.7601 179.6469
H8C2C3C4 178.527 178.3266 178.3228
H8C2C3C12 1.0618 0.4071 0.3771
C2C3C4C5 1.2533 1.4924 1.5607
C2C3C4CH9 177.2186 176.0853 175.9146
C12C3C4C5 178.6021 179.2736 179.3814
C12C3C4H9 0.1303 1.6959 1.9061
C2C3C12H13 40.851 27.6014 29.5104

(continued on next page)

220 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230

Table 1 (continued)

Geometrical parameter HF/6-311+G(d,p) B3LYP/6-311+G(d,p) B3PW91/6-311+G(d,p) Experimentala

C2C3C12HC14 137.9375 150.6185 148.6098
C4C3C12H13 136.5087 150.1887 148.3175
C4C3C12C14 44.7028 31.5914 33.5624
C3C4C5C6 0.1638 0.191 0.1899
C3C4C5H10 179.4749 179.2543 179.2292
H9C4C5C6 178.6435 177.7877 177.6787
H9C4C5H10 0.9952 1.6575 1.7405
C3C4H9H20 58.9896 56.787 58.0523
C5C4H9H20 122.5235 125.6021 124.4422
C4C5C6C1 0.8528 1.097 1.1434
C4C5C6H11 179.8294 179.8147 179.8016
H10C5C6C1 178.7843 178.3459 178.2735
H10C5C6H11 0.5336 0.7423 0.7816
C4H9H20C18 121.5081 115.245 117.0416
C3C12C14N15 177.7646 177.7817 177.9566
C3C12C14C18 3.1153 3.6536 3.7471
H13C12C14N15 3.4568 3.9944 3.9122
H13C12C14C18 175.6633 174.5702 174.3841
C12C14N15O16 10.3052 4.7168 3.807
C12C14N15O17 169.3824 174.8442 175.7782
C18C14N15O16 168.9565 174.076 174.7563
C18C14N15O17 11.3558 6.363 5.6584
C12C14C18H19 131.114 136.8325 135.5603
C12C14C18H20 11.5501 16.6287 15.3519
C12C14C18H21 109.4526 104.4019 105.7516
N15C14C18H19 48.0186 41.7482 42.7538
N15C14C18H20 167.5824 161.952 162.9621
N15C14C18H21 71.4148 77.0174 75.9344
C14C18H20H9 60.1861 64.2493 63.8393
H19C18H20H9 179.3527 174.7671 175.2399
H21C18H20H9 62.2879 58.629 59.0715
a
Ref. [7].
b
Ref. [8,9].

Fig. 3a. Geometrical parameter (bond length) of 1-phenyl-2-nitropropene.

NO2 vibrations
The characteristics group frequencies of the NO2 are usually
independent of the rest of the molecule. The nitro group vibrations
are generally associated with symmetric and anti-symmetric
stretching, in-plane bending vibrations which includes scissoring
and rocking, and the out of plane bending which includes the wag-
ging and twisting modes. The asymmetric stretching vibrations of
the NO2 group are assigned at 15701485 cm1 [18] and that of
symmetric vibrations at 13701320 cm1. Rajamani et al [19] have
identied the asymmetric stretching mode at 1570 cm1 in 4-nitro
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230
Fig. 3b. Geometrical parameter (bond angle) of 1-phenyl-2-nitropropene.
phenoxyphenyl. In the present compound, two NO2 stretching
vibrations have been observed at 1550 and 1520 cm1 which
shows that they are asymmetric in mode. The in-plane and out-
of-plane bending vibrations are found at 1010 & 980 cm1 and
660 & 580 cm1 respectively for NO2 group. The presence of the
NO2 bands in this molecule indicates that the stretching frequen-
cies are not inuenced whereas there is some mixing of CC vibra-
tions in bending frequencies.
CN vibrations
The mixing of several bands causes very difcult in the identi-
cation of CN vibrations in many molecules. Silverstein et al [20]
assigned the CN stretching in the region 13821266 cm1.In the
present molecule, the band is observed at 1430 cm1 for CN
stretching vibration. Frequency nearer to 1500 cm1 indicates
C@N while frequency nearer 1300 cm1 indicates the presence of
CN, in this case it lies in between these two values, which may
be due to the conjugation of electrons between the two adjacent
NO bonds with this CN bonds. Similarly, the in-plane and out-of-
plane vibrations are assigned at 900 and 520 cm1, respectively
for this CN which again has similar deviation noticed as in
stretching, which may also be due the conjugation of NO and CN
bonds.
Mullikan atomic charges
Mullikan atomic charges calculation has an important role as
the atomic charges cause the dipole moment, molecular polariz-
ability, electronic structure and molecular reactivity of the system.
The charges on the atoms of the present compound are calculated
by Mullikan population analysis using B3LYP method with 6-
311+G(d,p) basis set, the graphical representation of the results
are presented in Fig. 6. In the case of benzene ring, all the carbon
atoms are expected to be equally negative, but in this case atom
C3 is found to be highly positive which may be due to the attach-
ment of entire nitro propene group at this atom. C4 is also found to
be relatively more negative as some of the negative charge from C3
might have been repelled towards to this atom. But, all the hydro-
gen atoms in the benzene are found to be equally slightly positive
as expected as in other molecules.
221
In the case of propene group, there are three carbon atoms, of
which one (C14) is positive and the other C12 and C18 are equally
negative. The positive charge of C14 may be due to its attachment
with the NO2 group and the equal negative charge of C12 and C18
may be also due to the same reason, as these carbon atoms jointly
acts as a dipole. It is the charge distribution due to NO2 becomes
the reason for high negative charge of C3 in benzene. The C18 car-
bon atom is in methyl group, hence it has the chance to attract the
electrons from three hydrogen atoms, which shows the delicate
charge distribution among these carbon atoms C3C12C14C18.
The hydrogen atoms in this propene group are also equally posi-
tive, exactly similar to the hydrogen atoms in benzene group.
The charge distribution in NO2 group shows that all the three
atoms in this group are equally negative, which shows they have
equally divided the electrons withdrawn from C14.
Global softness and local region-selectivity
Besides the traditional reactivity descriptors, such as HOMO &
LUMO, there are certain other chemical reactivity descriptors such
as global hardness (g), global softness (S) local softness (DS), Fukui
function (f) global electrophilicity (x) and local electrophilicity
(Dx) [2124] which are dened by Koopmanss theorem [25,26]
as follows. The above descriptors are calculated using the formulae
cited in the previous works [27]. All these parameters are com-
puted using B3LYP method and 6-311+G(d,p) basis set and the val-
ues are presented in Tables 5 and 6. The global hardness value
(4.011 eV) in comparison with benzene (3.294 eV) shows that the
hardness is increased for this molecule due to the attachment of
nitro propene group. This is also reected in global softness value
which gets decreased from 0.3035 eV for benzene to 0.249 eV for
this molecule. The global electrophilicity value shows that it is
increased from benzene (2.096 eV) to 3.535 eV in this molecule.
This electrophilicity of this molecule is also found to increase fur-
ther in gas and ethanol phase.
In the case of local softness which indicate the reacting ten-
dency of the individual atoms; the values shows that local softness
is very high for C12 (0.3842 eV) and C4 (0.2758 eV) and minimum
for C3 and C14, which shows C12 and C4 are more prone to reac-
tions and C3 and C14 are highly inert. The electrophilicity index
222 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230

Table 2
Calculated scaled frequencies of 1-phenyl-2-nitropropene.

S.no. C1 symmetry species Observed frequency Calculated frequency Vibrational assignments

HF B3LYP B3PW91
FT-IR FT-Raman 6-311+G(d,p) 6-311+G(d,p) 6-311+G(d,p)
1 A0 3090w 3100 3100 3096 CH m
2 A0 3080w 3098 3098 3089 CH m
3 A0 3060w 3092 3092 3079 CH m
4 A0 3070w 3081 3081 3069 CH m
5 A0 3010w 3071 3071 3065 CH m
6 A0 2990w 3065 3065 3062 CH m
7 A0 2980w 3038 3038 3038 CH m
8 A0 2970w 3005 3005 3006 CH m
9 A0 2960w 2948 2948 2942 CH m
10 A0 1680m 1738 1738 1657 C@C m
11 A0 1630s 1653 1653 1594 C@C m
12 A0 1620m 1643 1643 1567 C@C m
13 A0 1580s 1621 1621 1562 C@C m
14 A0 1550s 1522 1522 1616 N@O m
15 A0 1520vs 1490 1490 1567 N@O m
16 A0 1505vs 1479 1479 1560 CC m
17 A0 1490s 1478 1478 1551 CC m
18 A0 1480s 1468 1468 1508 CC m
19 A0 1460s 1436 1436 1461 CC m
20 A0 1440m 1417 1417 1454 CC m
21 A0 1430w 1387 1387 1441 CN m
22 A0 1380vs 1412 1412 1415 CH b
23 A0 1350m 1377 1377 1317 CH b
24 A0 1330vs 1357 1357 1366 CH b
25 A0 1320vs 1296 1296 1342 CH b
26 A0 1300m 1256 1256 1272 CH b
27 A0 1270vs 1231 1231 1251 CH b
28 A0 1220m 1226 1226 1197 CH b
29 A0 1160m 1178 1178 1195 CH b
30 A0 1110w 1176 1176 1151 CH b
31 A0 1090m 1018 1018 1143 C@C b
32 A0 1010w 1004 1004 1057 N@O b
33 A0 980m 997 997 1047 N@O b
34 A0 970m 991 991 1018 CC b
35 A0 950m 956 956 984 CC b
36 A0 900w 906 906 947 CN b
37 A00 880m 877 877 906 CH d
38 A00 870m 823 823 889 CH d
39 A00 860m 786 786 823 CH d
40 A00 760s 755 755 775 CH d
41 A00 750w 715 715 756 CH d
42 A00 740m 700 700 743 CH d
43 A00 720s 710 710 787 CH d
44 A00 700w 684 684 756 CH d
45 A00 680s 613 613 680 CH d
46 A00 670m 718 718 642 C@C d
47 A00 660m 613 613 536 N@O d
48 A00 580s 587 587 517 N@O d
49 A00 570m 510 510 464 CC d
50 A00 540m 467 467 412 CC d
51 A00 520s 389 398 349 CN d
52 A0 510m 339 339 304 CCC b
53 A0 480w 298 298 246 CCC b
54 A0 450w 153 153 145 CCC b
55 A00 440w 123 123 107 CCC d
56 A00 420w 78 78 72 CCC d
57 A00 100m 48 48 43 CCC d

vs very strong; s strong; m medium; w weak; vw very weak, m stretching; b in-plane vibrations; d out-of-plane vibrations.

which shows the electron attracting ability of the individual atoms,
shows that C4 and C12 are highly electrophilic and C3 and C14 are
highly electrophobic which again explains the local softness and
hardness of these atoms, respectively.
NMR assessment
The chemical shifts for H and C atoms of the compound are
computed for optimized structure, supported by GIAO method
using B3LYP functional with 6-311+G(2d,p) basis set. The com-
puted values in gas and solvent phase are presented in the
Table 3 and graphical representation of the values are shown in
Figs. 7 and 8.
The aromatic carbon atoms generally have shifts in the range of
100150 ppm. Karunakaran et al. [28] have found the aromatic
carbons in 4-methyl propiophenone to have chemical shift
between 130 and 140 ppm and around 8 ppm for methyl group
carbon atom, respectively.
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 223

Fig. 4. Experimental [A] and calculate [B,C] FT-IR spectrum of 1-phenyl-2-nitro propene.

In the present compound the chemical shifts of the aromatic

carbon atoms, namely C1, C2, C3, C4, C5 and C6, almost lie in the
same rang, from 131 to 138 ppm. And in the case of substitution
group, the two carbon atoms C12 & C14 have values of 139 &
151 ppm, respectively. Among all the carbon atoms in the benzene
C3 is found to have relatively larger value 138 ppm which is the
carbon atom where the substitution group is attached with ben-
zene and found to be highly positive compared to other carbon
atoms. The C18 carbon atom which is present in the methyl group
is found to have extreme minimum value, around 12 ppm, which
shows the high shielding nature of three electrons in the methyl
group. The large value of C12 and C14 indicate relatively the large
magnitude of the charges associated with these atoms, though the
rst one is highly negative and latter is highly positive.
The chemical shifts of the hydrogen atoms are found almost
below 10 ppm, which show that the chemical environment of the
hydrogen atoms are not affected by oxygen or any carbon atoms.
Among this the methyl group proton are heavily shielded having
the values below 2 ppm, this trend is in tune with the literature
[28]. There is no appreciable difference observed in the chemical
shifts in different solvents phases. Hence the impact of the solvents
on the chemical shifts of the compound for various atoms is negli-
gibly small.

NBO, UVVis spectra and HOMOLUMO analysis

Fig. 5. Experimental [A] and calculate [B,C] FT-Raman spectrum of 1-phenyl-2- The electronic characteristics of the present compound 1-phe-
nitro propene. nyl-2-nitropropene are studied using TD-SCF B3LYP functional
224 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230
Fig. 6. Mullikan charge of 1-phenyl-2-nitropropene.
Fig. 7. Chemical shift of carbon atoms in gas and solvent phase.
with 6-311+G(d,p) basis set. The experimental spectrum of the
compound is also recorded and the same is presented along with
theoretical spectrum in Fig. 9. The other theoretical parameters
with the possible transitions are presented in Table 4. The NBO
output parameters such as occupancy, donors and acceptors, stabi-
lization energy, polarization energy etc are presented in Table 7.
The Table 7 shows the various possible donors and acceptors in
molecule with their occupancy value in each position, similarly
the various possible transitions among these donors and acceptors.
The stabilization energy for these transitions give a measure of the
probabilities of these transitions; which indicate the highly proba-
ble in this molecule are C1C2 to C3C4 (pp, 19.52 Kcal/mol),
C1C2 to C5C6 (pp, 20.60 Kcal/mol), C3C4 to C5C6 (pp,
19.82 Kcal/mol), C3C4 to C12C14 (pp, 11.78 Kcal/mol), C12
C14 to N15O17 (pp, 21.04 Kcal/mol), O16 to N15O17 (np,
159.57 Kcal/mol) and O17 to N15O16 (np, 18.62 Kcal/mol).
Fig. 8. Chemical shift of hydrogen atoms in gas and solvent phase.
Of which the most probable transition is np transition from
O16 to N15O17 (159.57 Kcal/mol), and the next probable transi-
tions are C12C14 to N15O17 (pp, 21.04 Kcal/mol), which takes
place within the substitution group and C1C2 to C5C6 (pp,
20.60 Kcal/mol), inside the benzene ring. Both are pp transitions.
Table 4 shows these three transitions in both gas and ethanol
phase, with corresponding energy difference between HOMO and
LUMO and the oscillator strengths. Here, the experimental spec-
trum is recorded in ethanol phase which shows only two peaks,
at 306 and 223 nm, respectively, these are corresponding to rst
two transitions; np and pp transitions which have consider-
ably high oscillator strengths (f). The HOMOLUMO contribution
for the rst transition is 99% which is the reason for very high sta-
bilization energy and oscillator for this transition.
The highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital are computed with B3LYP functional
with 6-311+G(d,p) basis set and the pictorial diagram of the
HOMOLUMO are shown in Fig. 10. And the energies of the
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 225

Fig. 9. UVVis spectra of 1-phenyl-2-nitropropene.

HOMOLUMO, energy gap and different reactivity descriptors of
molecule in both optimized and electronic transition levels are
presented in Table 5.
The energy gap of optimized benzene ring is 6.5886 eV, but by
the addition of the substitution propene and nitro group it is
widened by 8.023 eV, where the energy ow is low. On the con-
trary in the transition state, the gap is doubly shortened by
4.66 eV, which shows the possibility of high ow of energy from
HOMO to LUMO.
Similarly other descriptors of the molecule do vary from the
optimized to transition state and the values are presented in
Table 5. The electronegativity, which is a measure of attraction of
an atom for electrons in a covalent bond, has 3.71 eV in benzene
and 5.32 & 4.86 eV in optimized and electronic states, respectively.
226 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230

Table 5
Table 3
HOMO, LUMO, Kubo gap, global electronegativity, global hardness and softness,
Experimental and calculated 1H and 13
C NMR chemical shifts (ppm) of 1-phenyl-2-
global electrophilicity index of 1-phenyl-2-nitropropene.
nitropropene.
Parameters Benzene 1-Phenyl-2-nitropropanol
Atom Gas Chloroform Solvent-DMSO
ring
position TMS/B3LYP/6- TMS/B3LYP/6- TMS/B3LYP/6- Optimized state Transition state
311+G(2d,p) GIAO 311+G(2d,p) GIAO 311+G(2d,p) GIAO by TD-SCF
(ppm) (ppm) (ppm)
B3LYP/6- Gas Ethanol
1-C 131.457 131.643 131.661 311+G(d,p)
2-C 132.945 133.226 133.333
EHOMO (eV) (eV) 7.0101 9.338 7.1987 7.0537
3-C 138.08 137.467 137.341
ELUMO (eV) (eV) 0.4215 1.314 2.5358 2.6634
4-C 130.716 131.154 131.39
DEHOMOLUMO gap (eV) 6.5886 8.023 4.6629 4.3902
5-C 131.064 131.377 131.501
(eV)
6-C 131.511 132.346 132.595
Electronegativity (v) 3.7163 5.326 4.8673 4.8585
12-C 139.197 141.02 141.65
(eV)
14-C 151.271 152.027 152.419
Chemical hardness (g) 3.2943 4.011 2.3314 2.1951
18-C 12.1327 12.1353 12.1576
(eV)
7-H 7.3506 7.4682 7.5114
Global softness (r) (eV) 0.3035 0.249 0.2144 0.2277
8-H 7.2681 7.3794 7.4254
Electrophilicity index 2.0961 3.535 5.0806 5.3768
9-H 7.1849 7.3135 7.3758
(x) (eV)
10-H 7.3387 7.4645 7.5152
sDipole moment (l) 0.0001 5.513 5.0445 6.1105
11-H 7.2696 7.4085 7.4595
(Debye)
13-H 8.18 8.2723 8.3058
19-H 1.7532 1.7432 1.7323
20-H 1.8672 1.9727 2.0112
21-H 1.9742 2.0309 2.0531 optimized geometry [30,31]. The gure shows the negative charges
are more concentrated at the top of the nitro group, whereas the
blue region is spread over at the top of the hydrogen atoms of
The chemical hardness of benzene is 3.29 eV and substituted mole- the phenyl and propene hydrogen atoms and other regions are
cule is 4.01 and 2.33 eV in optimized and transition state, respec- found to be neither red nor blue [32], almost neutral. The color
tively, which shows that the present molecule is less stable code of these maps is in the range between 6.15 a.u. (deepest
compared to the benzene ring. The electrophilicity index is a mea- red) and 6.15 a.u. (deepest blue) in the compound. The positive
sure of lowering of total energy due to the maximal electron ow (blue) regions of MEP are related to electrophilic reactivity and
between the donors and the acceptors. The electrophilicity indices the negative (green) regions to nucleophilic reactivity.
of 1P2NP is 3.53 and 5.08 eV in optimized and transition state,
respectively, whereas benzene ring is 2.09 eV. This shows that
the electrophilicity index, which is the measure of the lowering Polarizability and rst order hyperpolarizability calculations
of total energy, is increased during transition [29].
The dipole moment in a molecule is another important elec- In order to investigate the relationships among molecular struc-
tronic property. The dipole moment of the benzene ring is almost tures and non-linear optic properties (NLO), dipole moment the
zero, whereas by addition of the propene and nitro group, dipole polarizability and rst order hyperpolarizability of the 1-phenyl-
moment of the present molecule is increased by 5.51 and 5.52 2-propene compound were calculated using B3LYP method with
Debye in optimized and transition state respectively, which shows 6-311+G(d,p) basis set.
the charge ow occur from negative to positive direction. The polarizability and hyperpolarizability tensors (axx, axy, ayy,
axz, ayz, azz and bxxx, bxxy, bxyy, byyy, bxxz, bxyz, byyz, bxzz, byzz, bzzz)
Molecular electrostatic potential (MEP) maps can be obtained by a frequency job output le of Gaussian.
However, a and b values of the Gaussian output are in atomic units
The molecular electrical potential surfaces from Fig. 11 illus- (a.u.), so they have been converted into electronic units (esu) (a;
trate the charge distributions of molecules three dimensionally. 1 a.u. = 0.1482  1024 esu, b; 1 a.u. = 8.6393  1033 esu). The cal-
This map allows us to visualize variably charged regions of a mole- culations of the total molecular dipole moment (l), linear polariz-
cule. The knowledge of the charge distributions can be used to ability (a) and rst-order hyperpolarizability (b) from the Gaussian
determine how molecules interact with one another and it is also output have been explained in detail previously.
used to determine the nature of the chemical bond. Molecular elec- The rst hyperpolarizability (b) and the components of hyper-
trostatic potential is calculated at the B3LYP/6-311+G(d,p) polarizability, by and bz of 1P2NP along with related properties

Table 4
Experimental and theoretical electronic absorption spectra of 1-phenyl-2-nitropropene (absorption wavelength k (nm), excitation energies E (eV) using TD-SCF/B3LYP/6-
311++G(d,p) method.

Experimental Theoretical Major contribution Assignment Region Bands

k (nm) E (eV) f TD-SCF
k (nm) E (eV) f
Gas
339.27 3.6545 0.0053 H2 ? LUMO (91%) n ? p Quartz UV R-band (German, radikalartig)
317.86 3.9006 0.2914 HOMO ? LUMO (95%) p ? p Quartz UV
295.99 4.1888 0.0058 H1 ? LUMO (93%) p ? p Quartz UV
Ethanol
306.5 1.238 349.21 3.5504 0.4767 HOMO ? LUMO (99%) n ? p Quartz UV R-band (German, radikalartig)
223.5 0.892 327.23 3.7889 0.0043 H2 ? LUMO (64%) p ? p Quartz UV
321.10 3.8612 0.0065 H3 ? LUMO (24%) p ? p Quartz UV
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 227

Table 6
Fukui function and global and local softness and electrophilicity of 1-phenyl-2-nitropropene.

Atoms f+ = (q + 1)  q f = q  (q  1) Df = (f+)  (f) DS = Dfrgs Dx = Dfxgei

1C 0.0462 0.2318 0.27811 0.0693 0.98337
2C 0.0775 0.0584 0.13600 0.0338 0.48088
3C 0.1968 1.3494 1.54626 0.3854 5.4674
4C 0.1573 0.9495 1.10684 0.2758 3.9136
5C 0.0649 0.1994 0.26436 0.0658 0.9347
6C 0.1234 0.1343 0.25778 0.0642 0.9114
7H 0.0451 0.1427 0.09753 0.0243 0.3448
8H 0.0426 0.1333 0.09066 0.0226 0.3205
9H 0.0111 0.1850 0.17387 0.0433 0.6148
10 H 0.0438 0.1347 0.09091 0.0226 0.3214
11 H 0.0543 0.1392 0.08488 0.0217 0.3001
12 C 0.2558 1.2857 1.5416 0.3842 5.4510
13 H 0.0415 0.1551 0.11364 0.0283 0.4018
14 C 0.1628 0.3685 0.53143 0.1324 1.8791
15 N 0.0235 0.3746 0.39823 0.0992 1.4081
16 O 0.1363 0.3907 0.52641 0.1312 1.8613
17 O 0.1138 0.3052 0.41904 0.1044 1.4816
18 C 0.0136 0.2267 0.24040 0.0599 0.8500
19 H 0.0476 0.1766 0.12901 0.0321 0.4562
20 H 0.0121 0.1689 0.15684 0.0390 0.5545
21 H 0.0485 0.2022 0.15372 0.0383 0.5435

DS = local softness, rgs global softness; Dx local electrophilic index, xgei global electrophilic index.

Table 7
Second order perturbation theory of Fock matrix in NBO basis of 1-phenyl-2-nitropropene.

Donor Type of Occupancy Acceptor Type of Occupancy Energy E(2) Energy difference E(j)  E(i) Polarized energy F(i,j)
bond bond (kcal/mol) a.u. a.u.
C1C2 r 1.97895 C1C6 r 0.01619 2.72 1.28 0.053
r C2C3 r 0.02307 3.08 1.26 0.056
r C3C12 r 0.02447 3.21 1.19 0.055
r C6H11 r 0.01363 2.41 1.14 0.047
p 1.66287 C3C4 p 0.02640 19.52 0.28 0.067
p C5C6 p 0.32763 20.60 0.28 0.068
C1C6 r 1.97960 C1C2 r 0.01455 2.75 1.28 0.029
r C2H8 r 0.01356 2.55 1.13 0.048
r C5C6 r 0.01616 2.58 1.28 0.051
C2C3 r 1.97189 C1C2 r 0.01455 2.74 1.27 0.053
r C3C4 r 0.02640 3.61 1.25 0.060
r C3C12 r 0.02447 2.29 1.17 0.046
C3C4 r 1.97225 C2C3 r 0.02307 3.65 1.25 0.060
r C4C5 r 0.01513 2.29 1.13 0.045
r C12H13 r 0.01758 1.20 1.13 0.033
p 1.62699 C1C2 p 0.30608 19.09 0.28 0.067
p C5C6 p 0.32763 19.82 0.28 0.067
p C12C14 p 0.12312 11.78 0.29 0.056
C3C12 r 1.97195 C1C2 r 0.01455 2.12 1.25 0.046
r C2C3 r 0.02307 2.22 1.22 0.047
r C3C4 r 0.01513 2.71 1.23 0.051
r C12C14 r 0.01975 4.02 1.31 0.065
r C14N15 r 0.11419 3.37 0.94 0.052
C4C5 r 1.97894 C3C4 r 0.02640 3.21 1.26 0.057
r C3C12 r 0.02447 3.68 1.19 0.059
r C5C6 r 0.01616 2.74 1.28 0.053
C5C6 r 1.97969 C1C6 r 0.01619 2.57 1.28 0.051
r C4C5 r 0.01513 2.48 1.14 0.053
p 1.64254 C1C2 p 0.30608 19.34 0.28 0.067
p C3C4 p 0.38064 21.46 0.28 0.070
C12H13 r 1.96362 C14N15 r 0.11419 2.43 0.78 0.040
r C14C18 r 0.01935 7.72 0.93 0.076
C12C14 r 1.97929 C2C3 r 0.02307 1.47 1.32 0.039
r C3C12 r 0.02447 3.37 1.25 0.058
r C14C18 r 0.01935 3.40 1.18 0.057
p 1.84794 C3C4 p 0.38064 8.24 0.32 0.048
p N15O17 p 0.62429 21.04 0.16 0.060
C14N15 r 1.98511 C3C12 r 0.02447 3.12 1.26 0.056
N15O17 p 1.98365 C12C14 p 0.12312 4.42 0.48 0.042
p N15O17 p 0.62429 7.16 0.32 0.051
O16 p 1.89351 C14N15 r 0.11419 13.09 0.55 0.076
p N15O17 r 0.05525 19.01 0.72 0.106
p N15O17 p 0.05525 159.57 0.14 0.138
O17 r 1.98149 C14N15 r 0.11419 3.97 1.06 0.059
r N15O16 r 0.05446 2.24 1.23 0.047
p 1.90287 C14N15 r 0.11419 11.92 0.55 0.073
p N15O16 r 0.05446 18.62 0.73 0.105
228 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230

(l0, atotal, and Da) are reported in Table 8. The calculated value of Table 8
the dipole moment is found to be 5.4317 Debye. The highest value The dipole moment (l) (Debye), polarizability (a) and rst hyperpolarizability (b) of
1-phenyl-2-nitropropene.
of the dipole moment is observed for component lx, which is equal
to 5.3973 D and the lowest value of the dipole moment of the Parameter a.u. Parameter a.u.
molecule for the component lc is 0.3513 D. The calculated average axx 85.7684 bxxx 98.8714
polarizability and anisotropy of the polarizability is 11.13  1024 axy 0.5686 bxyy 0.7144
esu and 6.7194  1024 esu, respectively. The hyperpolarizability ayy 61.7938 bxzz 0.9015
axz 1.7010 byyy 0.2319
b is one of the important key factors in NLO system. The B3LYP/ ayz 4.3390 byxx 1.2949
6-311+G(d,p) calculated rst hyperpolarizability value (b) is azz 77.8698 byzz 2.9415
840.373x1033 esu. From the values of dipole moment and hyper atot 11.13  1024 esu bzzz 1.6692
polarizability is approximately 3.955 D and 2.253  1033 esu Da 6.7194  1024 esu byyz 1.9810
times higher than those of urea (l and b of urea are 1.3732 D lx 5.3973 Debye bxxz 0.9015
ly 0.3513 Debye btot 840.3737  1033 esu
and 372.89  1033 esu) [33]. It is evident that the molecule consti- lz 0.4997 Debye
tute a better NLO material. ltot 5.4317 Debye

Thermodynamical parameters
Table 9
On the basis of vibrational analysis, the statically thermody- Thermodynamic properties at different temperatures at the B3LYP/6-311+G(d,p) level
of 1-phenyl-2-nitropropene.
namic functions: heat capacity C entropy S and enthalpy changes
DH for the title molecule were obtained from the theoretical T (K) Cm (cal mol1 K1) Sm (cal mol1 K1) DHm (cal mol1 K1)
harmonic frequencies and listed in Table 9. It is observed that 100 12.380 66.543 101.868
the thermodynamic functions are increasing with temperature 200 24.097 79.919 103.666
ranging from 100 to 600 K due to the fact that the molecular 300 37.514 93.033 106.747
400 49.639 106.109 111.123
vibrational intensities increase with temperature. The correlation
500 59.410 118.723 116.595
equations between heat capacity, entropy, enthalpy, and 600 67.064 130.622 122.934

Cm heat capacity; Sm Entropy; DHm Enthalpy.

Fig. 11. MEP map of 1-phenyl-2-nitropropene.

temperatures were tted by quadratic formulas and the corre-

sponding tting factors (R2) for these thermodynamic properties
are 0.99987, 0.9973, and 0.9999, respectively. The corresponding
tting equations are as follows and the correlation graphics are
shown in Fig. 12.

C 1:82705 0:01195 T 1:43685  106 T 2 R2 0:99858

S 0:29265 0:00191 T 2:67745  105 T 2 R2 0:9999

DH 0:2117 0:00139 T 1:93689  106 T 2 R2 0:9999

Fig. 10. Frontier molecular orbitals of 1-phenyl-2-nitropropene.
The conformers of this compound which was discussed in the
beginning of the paper based on the total energy of the molecule,
now have also been analyzed in terms of the other thermodynam-
ical parameters, by computing these parameters with B3LYP
functional and 6-311++G(d,p) basis set at room temperature. The
ve different conformers have been selected with scan coordinate
 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230 229

Table 10
Thermodynamic properties of different conformers at 300 k temperature the B3LYP/
6-311+G(d,p) level of 1-phenyl-2-nitropropene.

Conformer at (in DE DH (KCal/ Cv S

degree) (Hartree) Mol) (cal mol1 K1) (cal mol1 K1)
0 0.1681 106.747 37.514 93.033
80 0.1636 104.818 36.757 100.132
150 0.1642 104.194 34.583 91.952
220 0.1637 104.810 29.800 86.511
290 0.1643 105.877 35.327 91.389

Cv heat capacity; S entropy; DH Enthalpy, DE total energy.

Fig. 12. Correlation graph of heat capacity, entrophy and enthalphy with respect to
temperature.
of 0, 80, 150 220 and 290, of which the conformers at 80 and
220 gave the lowest energy conguration and at 0, 150 and
290 with highest energies. Fig. 13 shows the graph drawn for
the enthalpy, heat capacity and entropy for all these conformers.
These graphs depict some interesting results; the enthalpy is found
to be minimum only for conformer at 150 scan coordinate, which
is one of the highest energy conformer. The two minimum energy
conformers have intermediate enthalpy values, whereas two of the
highest energy conformer retain the highest enthalpy values while
third one to have the lowest enthalpy values. In the case of heat
capacity, the conformer at 220 has the lowest heat capacity value
while all the other four conformers have higher values. The
entropy also shows the minimum value for conformer at 220,
but with small change in the pattern of variation when compared
to heat capacity. All these thermodynamical parameters variation
shows a delicate balance between the molecular structure and

Fig. 13. Conformers vs thermodynamical properties in 1-phenyl-2-nitropropene.

230 S. Xavier, S. Periandy / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 216230
thermal properties. But the study of all these thermodynamical
properties for different conformers clearly reveals that the most
stable conformer among all the ve is conformer at 220 (Table 10).
Conclusion
By the conformational analysis, the stable conformer with low-
est energy is identied and same is used for further analysis. The
study of the molecular geometry reveals that there is no apprecia-
ble change in the bond length and bond angle of the molecule by
addition of the substitutional group. And most of the values are
closer to the experimental values.
On studying the vibrations of the compound, the CH out-of-
plane vibrations are inuenced by the other modes specically
NO and CC bending in-plane vibrations. And the CC vibrations
show good agreement with expected range. In the case of NO2,
stretching vibrations are not inuenced and the bending vibrations
are mixed with CC vibrations. Conversely, CN in-plane and out-of-
plane vibrations are again inuenced by NO and CC modes of
vibrations.
Mullikan and Fukui calculations have identied the negatively
and positively charged atoms in the molecule. In NMR analysis,
The chemical shifts of the aromatic carbon atoms are observed
within the expected range and substitutional carbon atom are
highly deshielded, whereas the methyl group carbon atom is heav-
ily shielded having very low chemical shifts.
In NBO analysis the most probable transitions are np transi-
tion from O16 to N15O17 (159.57 Kcal/mol), the next probable
transitions are C12C14 to N15O17 (pp, 21.04 Kcal/mol), which
takes place within the substitution group and C1C2 to C5C6 (p
p, 20.60 Kcal/mol), inside the benzene ring. The HOMOLUMO
energy gap and other reactivity descriptors of the molecule are
compared with optimized state of benzene ring. The energy gap,
chemical harness and electronegativity are found decreased with
the addition of the substitutional group, whereas the electrophilic-
ity index is increased. The values of the dipole moment, polariz-
ability and hyperpolarizability reveal that the present molecule is
good candidate for NLO material. The results of the thermo dynam-
ical parameters show that the parameters: entropy, enthalpy and
heat capacity increase with increase of the temperature.
Acknowledgements
We remain grateful to the Administration of St. Josephs college
of Arts and Science (Autonomous), Cuddalore for providing us the
Quantum Computational Research Lab for all the computational
works of the compound.
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