Molecular conformational analysis, vibrational spectra, NBO analysis and first hyperpolarizability of (2E)-3-phenylprop-2-enoic anhydride based on density functional theory calculations

Article abstract of DOI:10.1016/j.saa.2014.02.194

The conformational behavior and structural stability of (2E)-3-phenylprop-2-enoic anhydride were investigated by using density functional theory. Seventeen possible stable conformations of the title compound were determined and verified with their calcula

Full text of DOI:10.1016/j.saa.2014.02.194

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Molecular conformational analysis, vibrational spectra, NBO analysis
and first hyperpolarizability of (2E)-3-phenylprop-2-enoic anhydride
based on density functional theory calculations
Y. Sheena Mary a,b, K. Raju , C. Yohannan Panicker , Abdulaziz A. Al-Saadi , Thies Thiemann ,
Christian Van Alsenoy
a
b
c,
⇑
d
e,f
g
Department of Physics, Fatima Mata National College, Kollam, Kerala, India
Department of Physics, University College, Trivandrum, Kerala, India
Department of Physics, TKM College of Arts and Science, Kollam, Kerala, India
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
Graduate School of Interdisciplinary Engineering Sciences, Kyushu University, Fukuoka, Japan
United Arab Emirates University, Al Ain, United Arab Emirates
Department of Chemistry, University of Antwerp, B2610 Antwerp, Belgium
b
c
d
e
f
g
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
ꢀ
Conformational analysis is done and
seventeen possible conformations are
reported.
ꢀ
ꢀ
IR, Raman spectra and NBO analysis
were reported.
The wavenumbers are calculated
theoretically using Gaussian09
software.
ꢀ
ꢀ
The wavenumbers are assigned using
PED analysis.
The geometrical parameters are in
agreement with that of similar
compounds.
a r t i c l e i n f o
a b s t r a c t
Article history:
The conformational behavior and structural stability of (2E)-3-phenylprop-2-enoic anhydride were
investigated by using density functional theory. Seventeen possible stable conformations of the title com-
pound were determined and verified with their calculated vibrational frequencies being all positive. The
optimized molecular structure, vibrational wavenumbers, corresponding vibrational assignments of (2E)-
Received 23 December 2013
Received in revised form 24 February 2014
Accepted 25 February 2014
Available online 19 March 2014
3-phenylprop-2-enoic anhydride have been investigated experimentally and theoretically using Gauss-
ian09 software package. Potential energy distribution of normal modes vibrations was done using
GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within
the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delo-
Keywords:
FT-IR
FT-Raman
Cinnamic
calization has been analyzed using NBO analysis. The calculated first hyperpolarizability of the title com-
ꢂ30
pound is 12 ꢁ 10
esu and is 92.31 times that of the standard NLO material urea and the title compound
Hyperpolarizability
is an attractive object for future studies of nonlinear optical properties. MEP was performed by the DFT
method and the predicted infrared intensities and Raman activities have also been reported.
Ó 2014 Elsevier B.V. All rights reserved.
⇑
Corresponding author. Tel.: +91 9895370968.
E-mail address: cyphyp@rediffmail.com (C.Y. Panicker).
http://dx.doi.org/10.1016/j.saa.2014.02.194
386-1425/Ó 2014 Elsevier B.V. All rights reserved.
1

Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
639
O
Introduction
Cinnamic acid is a natural product, found in cinnamon oil and
butter, but it or its hydroxylate derivatives have also been found in
coffee [1], apples [2], citric fruits [3], honey bee propolis [4] and wine
CBrCl3
OH
PPh3 (2.2 eq.)
CH2Cl2
[
5]. Cinnamic acid is one of the products derived from shikimic acid
in the shikimate and phenylpropanoid pathways [6]. While
cinnamic acid has a long history of human use as a component of
plant derived scents and flavoring agent [7], it and its derivatives
have also been found to show pharmacological properties, including
hepatoprotective [8], antioxidant [9], and anti-diabetic activities
O
O
O
[
[
10] as well as inhibitory properties against bacterial [11] and fungi
12]. As more reactive compounds, cinnamic anhydrides have not
6
7%
been found extensively in nature, although there has been a recent
isolation of a trans-cinnamic anhydride from the stem bark of Cinna-
momumzeylanicum [13]. Again because of their reactivity, direct use
of cinnamic anhydrides as commercial products are few, but may
develop as a report on the synthesis and characterization of cin-
namic-3b-hydroxyolean-12-en-28-carboxylic anhydride as a novel
anti-malarial agent shows [14]. However, cinnamic anhydrides are
used extensively as reactive starting materials for the preparation
of cinnamates as flavoring agents and components in perfumes
and of cinnamic amides with such applications as sun blocking
ingredients in cosmetics [15,16] and compounds of medicinal use-
fulness [17,18]. Extensive is the utilization of cinnamic anhydrides
as starting materials in polymerization reactions [19,20]. Polymers
containing cinnamoyl moieties are used in a wide range of applica-
tions in emergingfields such as in advanced microelectronics [21], in
photolithography [22], as nonlinear optical materials [23], in inte-
grated circuit technology [24] and as photo curable coatings [25].
In view of the use of cinnamic anhydride as a co-polymer as well
as an additive in polymerizations towards these types of polymers,
the purpose of the present study is to understand the lowest energy
optimized structure of trans/trans-cinnamic anhydride and to
investigate its spectroscopic features. Another essential aim of this
study is the description of the nonlinear optical properties of the
compound, which will be given in addition to an NBO analysis.
Scheme 1. Pathway of the title compound.
Methodology
Fig. 1. FT-IR spectrum of (2E)-3-phenylprop-2-enoic anhydride.
Experimental
trans-cinnamic anhydride was prepared from cinnamic acid via
an Appel type reaction (PPh CBrCl ). As base, triethylamine [26] or
3 3
triphenylphosphine can be used. trans-Cinnamic anhydride: to a
solution of triphenylphosphine (630 mg, 2.4 mmol) in dry dichloro-
methane (8 mL) was added bromotrichloromethane (475 mg,
2
3
.4 mmol), and the resulting mixture was stirred at rate for
0 min. to give a reddish-brownish solution [27,28]. Thereafter, cin-
namic acid (296 mg, 2.0 mmol) is added, and the resulting mixture is
held at reflux for 25 min. Thereafter, triphenylphosphine (630 mg,
2
8
.4 mmol) is added, and the reaction mixture is held at reflux for
h. Then, the cooled solution is concentrated in vacuo and the con-
centrate is subjected to a rapid column chromatography on silica gel
CH Cl –hexane 2:1) to give cinnamic anhydride (225 mg, 67%) col-
(
2
2
orless crystals (scheme 1); mp. 139–140 °C (Lit. 136 °C) [27,28].
TheFT-IRspectrum (Fig. 1) wasrecorded using KBr pellets ona DR/
Jasco FT-IR 6300 spectrometer. The FT-Raman spectrum (Fig. 2) was
obtained on a Bruker RFS 100/s, Germany. For excitation of the spec-
trum the emission of Nd:YAG laser was used, excitation wavelength
1
064 nm, maximal power 150 mW, measurement on solid sample.
Computation
Since no there are no structural determinations found in the lit-
erature for cinnamic anhydride, detailed conformational analysis
Fig. 2. FT-Raman spectrum of (2E)-3-phenylprop-2-enoic anhydride.

6
40
Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
was performed in this study using. For meeting the requirements
of both accuracy and computing economy, theoretical methods
and basis sets should be considered. Density functional theory
has been proven to be extremely useful in treating the electronic
structure of the molecules. Gaussian09 program [29] was used to
carry out DFT calculations with Becke’s three-parameter hybrid
model and the Lee–Yang–Parr correlation functional (B3LYP)
method. The basis set 6-311++G(d,p), which is an effective level
with a reasonable cost to study fairly large organic molecules,
was utilized. Seventeen possible stable conformations of the title
compound were determined and verified with their calculated
vibrational frequencies being all positive. Molecular geometries
were fully optimized by Berny’s optimization algorithm using
redundant internal coordinates. As the DFT hybrid B3LYP func-
tional tends to overestimate the frequencies of the fundamental
modes; scaling factors have to be used for obtaining a considerably
better agreement with experimental data. Thus, a scaling factor of
Syn-tt-tt
0
.9613 has been uniformly applied to the B3LYP calculated wave-
numbers [30]. The observed disagreement between theory and
experiment could be a consequence of the anharmonicity and of
the general tendency of the quantum chemical methods to overes-
timate the force constants at the exact equilibrium geometry. The
assignments of the calculated wave numbers are aided by the
animation option of GAUSSVIEW program, which gives a visual
presentation of the vibrational modes [31]. The potential energy
distribution (PED) values were calculated with the help of
GAR2PED software package [32].
Syn-ct-tt
Results and discussion
Conformational stability
Anti-tt-tt
Fig. 3. The optimized structures of the three most stable conformations in cinnamic
anhydride. Atom numbering for the most stable form (syn-tt-tt) is shown.
Molecular geometry plays a major role in determining the
structure–activity relationship. Moreover, conformational analysis
of the molecule provides meaningful information relevant to drug
actions. Since there are no structural determinations found in the
literature for cinnamic anhydride, a meticulous analysis was per-
formed in this study to understand the conformational behavior
of the molecule in the gas phase and to locate the possible global
minima. Results of geometry optimizations indicate that the title
compound is a rather flexible molecule along the A(OC)AOA(CO)
linkage and in theory could result with at least seventeen possible
conformers as shown in Fig. S1 (Supporting information). The three
most stable forms (less than 1 kcal/mol energy difference) are
shown in Fig. 3, while the relative stabilities for all forms are listed
in Table 1. Due to the many conformational possibilities of the
molecule, syn/anti and cis/trans notations have been adopted to ex-
plain the different configurations. Syn and anti configurations refer
to the relative positions of the two carbonyl groups whether they
are syn or anti with respect to each other. The tt (or trans–trans)
form is determined by the orientations of hydrogen atoms con-
nected to the C@C bond. For example for the most stable form
Table 1
Relative stabilities of possible conformations of cinnamic anhydride as predicted at
the B3LYP/6-311++G(d,p) level of theory.
Conformation
Total E (Hartree)
Relative E (kcal/mol)
Syn-tt-tt
Syn-ct-tt
Syn-ct-ct
Syn-tc-tt
Syn-tc-ct
Syn-ct-cc
Syn-cc-tt
Syn-tc-tc
Syn-tc-cc
Syn-cc-cc
Anti-tt-tt
Anti-ct-tt
Anti-tc-tt
Anti-cc-tt
Anti-ct-cc
Anti-tc-tc
Anti-tc-cc
ꢂ920.26172600
ꢂ920.26125871
ꢂ920.26069260
ꢂ920.25442781
ꢂ920.25387870
ꢂ920.25136450
ꢂ920.24977920
ꢂ920.24709700
ꢂ920.24432590
ꢂ920.23999250
ꢂ920.26108432
ꢂ920.26048997
ꢂ920.25322891
ꢂ920.2496486
ꢂ920.2485757
ꢂ920.2453696
ꢂ920.2420215
0.000
0.293
0.648
4.580
4.924
6.502
7.497
9.180
10.919
13.638
0.403
0.776
5.332
7.579
8.252
10.264
12.365
(Fig. 3), the tt configuration implies that H33 is trans to the C@O
group while H32 is trans to H33. The syn-tt-tt form was found to
be the most stable form.
Generally, cinnamic anhydride tends to take the tt-tt configura-
tion as it minimize the steric effect and enhance the pronounced
conjugation on the two sides of the molecule. This is in agreement
with the stable structure of the parent cinnamic acid molecule
where the trans- form is the most stable one. [33]. However, it is
also observed from the calculations that a number of the ct config-
urations, such as syn-ct-tt and anti-ct-tt, are greatly stabilized by
the very weak intra molecular hydrogen bonding between the cen-
Furthermore, for more insight on the conformational changes of
cinnamic anhydride, the internal rotations governing the inter-
changes between the three most stable forms have been investi-
gated at the B3LYP/6-311++G(d,p) level of theory. Fig. 4 depicts
the potential energy scan of the internal rotation about the central
CAOAC@O bond for the tt-tt structure. The syn form is clear to be
about 0.4 kcal/mol more stable than the anti form. In both forms,
the molecule tends to deviate from the planarity by approximately
30° to minimize the lone pair-lone pair repulsion between the cen-
tral and carbonyl oxygen atoms. Nevertheless, the syn-anti barrier
3
tral sp oxygen atom and either H33 or H34 atoms (Fig. S2, Support-
ing material). In the case of the syn-tt-tt form this distance is
approximately 2.3 Å.

Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
641
ꢂ1
Mariappan and Sundaraganesan [39] reported 1760 cm in the
ꢂ1
IR spectrum and 1764 cm
in the Raman spectrum as C@O
stretching mode for phenyl carbonate derivative.
The CAOAC stretching vibrations are expected in the ranges
ꢂ1
ꢂ1
1
200–1100 cm (asymmetric) and 1050–950 cm (symmetric)
[
3
34,40]. The skeletal CAO deformation can be found in the region
ꢂ1
20 ± 50 cm [41]. As expected the asymmetric CAOAC vibration
ꢂ1
is assigned at 1101 cm in the Raman spectrum with DFT value at
1
9
ꢂ1
102 cm . The symmetric CAOAC stretching vibration is assign at
ꢂ1
40 cm theoretically for the title compound [36]. Arjunan et al.
ꢂ1
ꢂ1
[
38] reported the bands at 1262 cm in IR and 1267 cm in Ra-
man as the CAOAC asymmetric stretching modes and the symmet-
ꢂ1
ꢂ1
ric CAOAC stretching mode at 924 cm in IR and 920 cm in
Raman spectrum. The deformation modes of CAOAC are reported
Fig. 4. The potential energy scan of the internal rotation about the central
CAOAC@O bond for the tt-tt structure.
ꢂ1
at 604, 606, and 287 cm experimentally [38].
According to Socrates [42] the C@C stretching is expected around
ꢂ1
1
600 cm when conjugated with C@O group. For the title com-
ꢂ1
pound, the bands observed at 1620 cm in the IR spectrum, 1621,
was predicted to be very low (about 1 kcal/mol). On the other
hand, the calculated barrier of the syn-tt-tt M syn-ct-tt inter con-
version (Fig. 5) was as high as 8 kcal/mol, indicating that a pro-
nounced conjugation effect exists along both sides of the molecule.
ꢂ1
ꢂ1
1
601 cm in the Raman spectrum and at 1611, 1607 cm theoret-
ically are assigned as C@C stretching modes. For the title compound,
the CH modes associated with the anhydride group are assigned at
ꢂ1
3
3
080, 3035, 3025, 1184, 870, 857 cm in the IR spectrum and at
ꢂ1
028, 1189, 870, 859 cm in the Raman spectrum.
The existence of one or more aromatic rings in a structure is
normally readily determined from the C@CAC ring related modes
IR and Raman spectra
and CAH vibrations. The CAH stretching modes occurs above
The observed IR and Raman bands and calculated (scaled)
wavenumbers and assignments are given in Table 2. The appear-
ance of strong bands in the IR and weak bands in the Raman spec-
tra (less polarizability resulting due to highly dipolar carbonyl
bond) in aromatic compounds is the salient feature of the presence
of carbonyl group and are due to the C@O stretching motions. The
wavenumber of the C@O stretch due to carbonyl group mainly de-
pends of the bond strength, which in turn depends upon inductive,
conjugative, steric effects and lone pair of electron on oxygen. The
carbonyl stretching C@O vibration [34–36] is expected in the re-
ꢂ1
3
000 cm and is typically exhibited as a multiplicity of weak to
moderate bands, compared with the aliphatic CAH stretch [43].
For the explanation of the phenyl ring modes, the rings C21AC22-
AC23AC24AC25AC26 and C AC AC AC AC AC are designated at
1 2 3 4 5 6
PhI and PhII in the following discussion. In the present case, the
DFT calculations give phenyl CH stretching modes in the range
ꢂ1
ꢂ1
3
042–3070 cm . The bands observed at 3062 cm in the IR spec-
ꢂ1
trum and at 3041, 3061 cm in the Raman spectrum are assigned
as the CH stretching modes of the phenyl rings. There are six ring
stretching modes for the benzene ring, of which the four with the
ꢂ1
gion 1750–1680 cm and in the present case these modes appears
ꢂ1
ꢂ1
highest wavenumebrs (occurring respectively near 1600, 1580,
at 1768, 1701 cm in IR spectrum, 1763, 1697 cm in Raman
ꢂ1
1
490 and 1440 cm ) are good group vibrations. In the absence
spectrum. The DFT calculations give these modes at 1768 and
ꢂ1
ꢂ1
of ring conjugation, the band near 1580 cm is usually weaker
1
702 cm . The in-plane and out-of-plane C@O deformations are
ꢂ1
ꢂ1
than that at 1600 cm . The fifth ring stretching mode is active
expected in the regions 625 ± 70 and 540 ± 80 cm , respectively
ꢂ1
near 1355 ± 35 cm , a region which overlaps strongly with that
[
8
7
34]. The dC@O in-plane deformation bands are observed at
ꢂ1
of the CH in-plane deformation [34,44]. The sixth ring stretching
04 cm in the IR spectrum, 779 in the Raman spectrum and at
ꢂ1
ꢂ1
ꢂ1
mode or ring breathing mode appears near 1000 cm in mono
99, 771 cm theoretically. The band observed at 697 cm in
ꢂ1
substituted benzenes [34]. The bands observed at 1577, 1551,
the Raman spectrum and at 691, 653 cm (DFT) are assigned as
ꢂ1
1
466, 1450, 1428, 1304 cm
in the IR spectrum and at 1579,
c
C@O modes. Cinar and Karabacak [37] reported the bands at
ꢂ1
ꢂ1
1535, 1485, 1430 cm in the Raman spectrum are assigned the
1
697 in IR, 1700 in Raman and 1684 cm (theoretical) is assigned
phenyl ring stretching modes. As seen from the table 2, the DFT
as C@O stretching mode. Arjunan et al., [38] reported C@O modes
ꢂ1
ꢂ1
calculations give these modes [34] in the range 1575–1299 cm
.
at 1776, 1716, 864, 723 cm
in the IR spectrum and at 673,
ꢂ1
ꢂ1
The ring breathing modes are observed at 994 cm in the IR spec-
trum and at 1003 cm in the Raman spectrum and theoretical val-
3
25 cm
in the Raman spectrum for an anhydride derivative.
ꢂ1
ꢂ1
ues are 1008 and 1007 cm as expected [34].
The CH out-of-plane deformations [34] are observed between
ꢂ1
1
000 and 700 cm . Generally, the out-of-plane CH deformations
with the highest wavenumbers have a weaker intensity than
those at lower wavenumbers. For the title compound, the out-
ꢂ1
of-plane CH deformation at 757 cm and the out-of-plane ring
ꢂ1
deformation at 691 cm in the IR spectrum form a pair of strong
bands characteristics of mono substituted benzene derivative
[
34,44]. The benzene CH in-plane bending are normally expected
ꢂ1
above 1000 cm and in the present case, the in-plane CH defor-
mations of the phenyl rings are obtained at 1320, 1161, 1131,
1
ꢂ1
ꢂ1
068 cm in the IR spectrum and at 1325, 1306, 1165 cm in
the Raman spectrum for the title compound. The DFT calculation
ꢂ1
gave these modes in the range 1062–1312 cm . Most of the
modes are not pure, but contains significant contribution from
other modes also.
Fig. 5. The calculated barrier of the syn-tt-tt M syn-ct-tt interconversion.

6
42
Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
Table 2
Vibrational assignments of (2E)-3-phenylprop-2-enoic anhydride.
B3LYP/6-311++G(d,p)
IR
–
Raman
–
Assignments
–
t
IR
I
R
A
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
9
9
9
9
9
9
9
9
9
9
8
8
8
8
8
8
8
7
7
7
7
6
6
6
6
6
6
077
076
070
070
064
064
055
055
047
047
042
042
027
027
768
702
611
607
575
575
551
551
467
467
423
422
312
310
302
299
285
282
261
251
181
181
158
158
139
139
102
062
062
018
008
007
83
83
76
75
64
64
48
48
40
07
99
99
62
56
29
17
16
99
71
51
38
91
77
69
53
49
09
10.90
4.65
3.00
17.72
11.59
27.76
12.76
7.41
0.06
0.04
2.54
2.84
114.91
34.51
541.62
48.86
112.52
5.98
67.02
160.27
171.67
63.17
9.67
14.97
48.06
15.20
464.04
80.29
4028.39
395.85
2515.13
514.82
119.02
11.57
108.11
12.24
39.93
32.55
52.32
14.51
9.22
3080
–
–
–
–
–
–
3061
3061
–
–
–
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
t
CH(86)
CH(86)
CHI(44),
CHI(44),
CHI(41),
CHI(41),
CHI(52),
CHI(45),
CHI(49),
CHI(46),
CHI(50),
CHI(44),
CH(97)
CH(97)
C@O(80)
C@O(82)
C@C(54),
C@C(54),
t
t
t
t
t
t
t
t
t
t
CHII(44)
CHII(44)
CHII(41)
CHII(41)
CHII(45)
CHII(52)
CHII(47)
CHII(49)
CHII(44)
CHII(50)
–
3062
3062
–
–
–
–
–
–
3035
3025
1768
1701
1620
–
1577
1577
1551
1551
1466
1450
1428
1428
1320
–
–
3041
3041
3028
3028
1763
1697
1621
1601
1579
1579
1535
1535
1485
1485
1430
–
0.67
0.35
411.74
139.25
67.83
645.45
10.01
48.54
0.19
41.62
0.63
15.72
18.24
21.53
3.89
25.62
0.63
62.09
0.50
109.74
0.94
133.73
42.29
1.67
1.56
20.26
0.00
2.00
2.55
9.29
6.43
2439.33
0.79
242.23
9.57
t
t
PhI(11),
PhI(13),
t
t
PhII(11)
PhII(12)
PhI(41),
PhI(33),
PhI(32),
PhI(31),
PhI(30),
PhI(31),
t
PhII(41)
PhII(33)
PhII(32)
PhII(31)
PhII(30)
PhII(31)
t
t
t
t
t
dCHI(10), dCHII(10),
dCHI(11), dCHII(11),
dCHI(28), dCHII(28) dCH(20)
dCHI(25), dCHII(25)
t
t
PhI(33),
PhI(35),
t
t
PhII(33)
PhII(35)
1325
1306
–
–
–
1304
–
–
t
PhI(38),
t
PhII(38)
9.30
280.62
0.26
dCH(16),
dCH(56), dCHI(15)
dCH(46), dCHII(14)
t
t
t
t
dCHI(28), dCHII(44)
dCHI(36), dCHII(36)
dCHI(38), dCHII(38)
dCHI(37), dCHII(37)
t
t
t
PhI(29), tPhII(29)
–
–
227.78
10.94
41.98
240.41
342.36
24.65
25.08
7.23
293.94
0.83
1.46
82.09
59.37
20.76
4.21
1260
1260
1184
1184
1161
1161
–
1131
–
1068
1068
–
–
994
–
–
–
1268
–
CC(18), dCHI(25), dCHII(25)
CC(24), dCHI(25), dCHII(25)
CC(17), dCH(28),
CC(18), dCH(28),
1189
1189
1165
1165
–
–
1101
–
t
t
PhI(11),
PhI(11),
t
t
PhII(11)
PhII(12)
CO(34), CC(32), dCH(18)
PhI(17), tPhII(17), dCHI(22), dCHII(22)
t
–
dCHI(25), dCHII(25)
1025
1003
1003
–
–
–
–
–
–
–
–
–
–
895
895
870
859
828
–
–
–
779
–
–
697
–
–
–
–
t
t
t
c
c
c
c
c
c
c
c
t
t
c
c
c
c
CO(34),
PhI(29),
PhI(28),
CH(46), dCC(30)
CH(46), dCC(30)
CHI(39),
CHI(37),
CHI(37),
CHI(37),
CHI(45),
CHI(46),
CO(46),
tCC(30)
t
PhII(29)
tPhII(28)
51.20
0.07
84.08
3.47
0.66
0.00
0.04
490.15
8.01
0.01
0.91
0.55
220.03
22.20
0.18
0.55
0.09
0.02
0.50
19.96
1.14
0.15
18.91
3.56
2.42
1.06
0.04
36.34
29.25
2.27
31.31
4.08
c
c
c
c
c
c
CHII(37)
CHII(39)
CHII(37)
CHII(37)
CHII(46)
CHII(46)
–
–
–
–
–
950
911
893
893
870
857
825
–
–
804
–
757
729
691
674
–
tCC(18)
CO(29), dCC(29)
CHI(38),
CHI(38),
CH(62),
CH(64),
c
c
CHII(38)
CHII(38)
3.70
c
c
C@O(14)
C@O(10)
43.25
48.05
0.37
3.12
3.56
3.69
97.78
6.85
65.66
17.31
48.68
0.00
13.72
0.02
dPhI(26), dPhII(26), tCC(36)
c
c
CHI(48),
CHI(48),
c
c
CHII(48)
CHII(48)
dCO(30), dC@O(43)
dC@O(42), PhI(13),
CHI(32), CHII(32),
PhI(35), PhII(35)
C@O(35), PhI(30),
s
c
s
sPhII(11)
c
c
s
c
CC(19)
s
sPhII(32)
7.05
1.02
16.69
0.91
15.55
s
s
PhI(21),
PhI(30),
s
s
PhII(21),
PhII(30),
c
c
CHI(18),
CHI(12),
c
c
CHII(18)
CHII(12)
–
645
–
c
c
C@O(28), sPhI(21), sPhII(21)
C@O(26), dC@O(22)
618
dPhI(43), dPhII(43)

Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
643
Table 2 (continued)
B3LYP/6-311++G(d,p)
t
IR
–
Raman
–
Assignments
–
IR
I
R
A
6
5
5
4
4
4
4
3
3
3
2
2
2
2
1
1
1
1
08
64
38
93
74
74
54
96
96
19
68
68
66
31
78
61
53
21
1.77
2.46
96.31
8.23
2.94
13.78
2.39
0.04
0.00
1.31
0.26
1.94
0.02
3.17
1.04
0.10
2.43
0.01
0.18
3.76
6.75
0.43
0.23
0.08
0.18
0.42
0.01
0.01
1.01
2.37
0.11
2.18
1.45
0.76
2.90
3.24
3.87
1.24
–
598
558
–
485
–
dPhI(43), dPhII(43)
dPhI(30), dPhII(30)
dC@O(30), dPhI(18), dPhII(18)
dCC(39), dCO(20)
560
555
488
–
s
s
PhI(22),
PhI(21),
s
s
PhII(22),
PhII(21),
c
c
CC(32)
CC(30)
–
–
–
456
405
–
–
–
–
–
–
–
–
–
–
–
dCC(46), dC@C(10)
400
400
328
272
–
–
–
–
–
s
s
PhI(42),
PhI(41),
s
s
PhII(41)
PhII(42)
dCC(43), dCO(15)
s
s
PhI(24),
PhI(24),
s
s
PhII(24)
PhII(24)
dCO(43), dC@C(11), dCC(29)
dCC(33), dC@C(15), dC@O(12)
dCC(33), dCO(20)
dCO(31), dCC(10), dC@C(10)
–
122
–
s
s
CO(35),
CC(27),
s
C@O(20),
sC@C(15)
s
s
CO(17), C@C(20)
CC(12),
s
9
2
c
CC(20),
CO(11),
dC@C(32), dCC(27)
CC(20), CC(18), dC@C(11), dCC(11)
dCC(36), dC@C(28)
C@O(21), CO(21),
dCO(31), C@O(16),
CC(26)
C@O(30)
s
sC@O(11)
9
8
5
4
1
1
1
2
4
1
9
5
8
0.18
0.81
0.04
0.94
0.78
0.01
0.23
0.54
1.50
4.70
0.52
4.39
8.68
1.76
–
–
–
–
–
–
–
89
–
–
–
–
s
c
s
s
s
s
C@C(17),
CO(16), dCC(17)
sCC(12)
s
–
–
s
s
C@C(35),
CO(30),
s
s
t
– stretching; d – in-plane deformation;
c
– out-of-plane deformation;
s
– torsion; PED contribution is given % in the assignments in brackets; IR
I
A
– IR intensity; R – Raman
activity; The rings C21AC22AC23AC24AC25AC26 and C
1
AC
2
AC
3
AC
4
AC
5
6
AC are designated at PhI and PhII.
ꢃ
NBO analysis
conjugative interaction of C17AO18 from of n
2
(O16) ?
p
(C17AO18
)
which increases ED (0.23391 e) that weakens the respective bonds
ꢂ1
In NBO analysis, the input atomic orbital basis set is transformed
via natural atomic orbital and natural hybrid orbital into natural
bond orbital. The NBOs obtained in this fashion correspond to the
widely used Lewis picture, in which two center bonds and lone pairs
localized [45]. The natural bond orbital (NBO) calculations were
performed using NBO 3.1 program [46] as implemented in the
Gaussian09 package at the DFT/B3lYP level in order to understand
various second order interactions between the filled orbital of one
subsystem and vacant orbital of another subsystem. In the NBO
analysis, the electronic wave functions are interpreted in terms of
a set of Lewis and a set of non-Lewis localized orbital [47]. Delocal-
ization effects can be identified from the presence of off diagonal
elements of the Fock matrix in the NBO basis. The output obtained
by the second order perturbation theory analysis is normally the
first to be examined by the experience NBO user in searching for sig-
nificant delocalization effects. However the strength of these delo-
calization interactions E(2) are estimated by the second order
perturbation theory as estimated by the equation.
leading to stabilization of 32.84 kcal mol . Another hyper conju-
ꢃ
gative interaction of O16AC17 from of n
2
(O18) ?
r
(O16AC17) which
increases ED (0.12612 e) that weakens the respective bonds lead-
ing to stabilization of 41.96 kcal mol . These interactions are ob-
ꢂ1
served as an increase in electron density (ED) in CAO anti
bonding orbital that weakens the respective bonds. The increased
electron density at the chlorine, oxygen, atoms leads to the elonga-
tion of respective bond length and a lowering of the corresponding
stretching wavenumber. The electron density (ED) is transferred
ꢃ
ꢃ
from the n(O), n(Cl) to the anti-bonding
p , r orbital of the CAO
explaining both the elongation and the red shift. The C@O, CAOAC
stretching modes can be used as a good probe for evaluating the
bonding configuration around the corresponding atoms and the
electronic distribution of the molecule.
The NBO analysis also describes the bonding in terms of the nat-
ural hybrid orbital n
(ꢂ0.27791 a.u.) with considerable p-character (99.96%) and low
occupation number (1.83971 a.u.) and the other n (O15) occupy a
2
(O15), which occupy a higher energy orbital
1
lower energy orbital (ꢂ0.67098) with p-character (41.78%) and high
2
ðFi;j
Þ
occupation number (1.97551 a.u.). Also n (O ), which occupy a
2
16
Eð2Þ ¼
D
Eij ¼ qi
ðE
j
ꢂ E
i
Þ
higher energy orbital (ꢂ0.35036 a.u.) with considerable p-character
100.0%) and low occupation number (1.78650 a.u.) and the other
(O16) occupy a lower energy orbital (ꢂ0.54245) with p-character
64.39%) and high occupation number (1.94037 a.u.). Again
(O18), which occupy a higher energy orbital (ꢂ0.27790 a.u.) with
considerable p-character (99.96%) and low occupation number
(
i i j
q is the donor orbital occupancy; E , E is diagonal elements and Fij
the off diagonal NBO Fock matrix element
n
1
(
In NBO analysis large E(2) value shows the intensive interaction
between electron-donors and electron-acceptors and greater the
extent of conjugation of the whole system, the possible intensive
interactions are given in Table S1 as Supporting material. The sec-
ond-order perturbation theory analysis of Fock matrix in NBO basis
shows strong The strong intra molecular hyper conjugative inter-
action of C14AO16 from of n
ED (0.12611 e) that weakens the respective bonds leading to stabil-
ization of 41.96 kcal mol . The strong intra molecular hyper
n
2
(
(
(
1
1.83970 a.u.) and the other n (O18) occupy a lower energy orbital
ꢂ0.67098) with p-character (41.78%) and high occupation number
1.97552 a.u.). Thus, a very close to pure p-type lone pair orbital par-
ꢃ
ticipates in the electron donation to the
r
(CAO) orbital for n2-
ꢃ
2
(O15) ?
r
(C14AO16) which increases
(
O
15) ?
r
ꢃ
(C14AO16),
r
ꢃ
(CAO) orbital for n
(O18) ?
r
ꢃ
(O16AC17),
2
ꢃ
ꢃ
p
(CAO) orbital for n
2
(O16) ?
p
(C17AO18) interactions in the com-
ꢂ1
pound. The results and tabulated in Table S2 as Supporting material.

6
44
Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
First hyperpolarizability
The nonlinear optical activity provide the key functions for fre-
quency shifting, optical modulation, optical switching and optical
logic for the developing technologies in areas such as communica-
tion, signal processing and optical interconnections [48,49]. The
0
first static hyperpolarizablity (b ) is calculated at the DFT level
based on the finite field approach. In the presence of an applied
electric field, the energy of a system is a function of the electric
field and the first hyperpolarizability is a third rank tensor than
can be described by 3 ꢁ 3 ꢁ 3 matrix. The 27 components of the
3
D matrix can be given in the lower tetrahedral format and re-
duced to 10 components because of Kleinman symmetry [50].
The components of b are defined as the coefficients in the Taylor
0
series expansion of the energy in the external electric field. When
the external electric field is weak and homogeneous, this expan-
sion is given below:
X
X
X
liF ꢂ 1
a
ijF F ꢂ
1
6
b F F F
i
i
j
i j k
E ¼ E
0
ꢂ
Fig. 6. HOMO and LUMO plots of (2E)-3-phenylprop-2-enoic anhydride.
ijk
2
i
ij
ijk
X
1
i
j k l
ꢂ 2
cijklF F F F þ ꢄ ꢄ ꢄ
4
ijkl
2/2
power of a ligand as
x
=
l
g. This index measures the stabiliza-
tion in energy when the system acquired an additional electronic
charge from the environment. Electrophilicity encompasses both
the ability of an electrophile to acquire additional electronic
charge and the resistance of the system to exchange electronic
charge with the environment. It contains information about both
electron transfer (chemical potential) and stability (hardness) and
where E
the origin,
0
is the energy of the unperturbed molecule, F
i
is the field at
l
i
,
a
i
, bijk and ijkl are the components of dipole moment,
c
polarizability, the first hyperpolarizabilities, and second hyperpo-
larizabilities, respectively. The calculated first hyperpolarizability
ꢂ30
of the title compound is 12 ꢁ 10
esu which is comparable with
that of similar derivatives [51–53] and is 92.31 times that of the
ꢂ30
is a better descriptor of global chemical reactivity. The hardness
g
standard NLO material urea (0.13 ꢁ 10
esu) [54]. We conclude
and chemical potential are given by the following relations:
l
that the title compound is an attractive object for future studies
of nonlinear optical properties.
g
= (I ꢂ A)/2 and
l
= ꢂ(I + A)/2, where I and A are the first ioniza-
tion potential and electron affinity of the chemical species [63].
For the title compound, EHOMO = ꢂ9.33 eV, ELUMO = ꢂ5.95 eV,
Frontier molecular orbital
energy
gap = HOMO–LUMO = 3.38 eV,
Ionization
potential
I = 9.33 eV, Electron affinity A = 5.95 eV, global hardness
= 1.69 eV, chemical potential
= ꢂ7.64 eV and global electro-
= 17.27 eV. It is seen that the chemical potential
To explain several types of reaction and for predicting the
most reactive position inconjugated systems, molecular orbital
and their properties such as energy are used [55]. The highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) are the most important orbital in a
molecule. The eigen values of HOMO and LUMO and their energy
gap reflect the biological activity of the molecule. A molecule hav-
ing a small frontier orbital gap is more polarizable and is gener-
ally associated with a high chemical reactivity and low kinetic
stability [56–58]. HOMO which can be though as the outer orbital
containingelectrons, tend to give these electrons as an electron
donor and hence the ionization potential is directly related to
the energy of the HOMO. On the other hand LUMO can accept
electrons and the LUMO energy is directly related to electron
affinity [59,60]. Two important molecular orbital were examined
for the title compound, HOMO and LUMO which are given in
g
l
2
philicity =
l /2g
of the title compound is negative and it means that the com-
pound is stable. They do not decompose spontaneously into the
elements they are made up of. The hardness signifies the resis-
tance towards the deformation of electron cloud of chemical sys-
tems under small perturbation encountered during the chemical
process. The principle of hardness works in Chemistry and phys-
ics but it is not physically observable. Soft systems are large and
highly polarizable, while hard systems are relatively small and
much less polarizable.
Molecular electrostatic potential
Molecular electrostatic potential (MEP) generally present in the
space around themolecule by the charge distribution is very useful
in understanding the sites of electrophilic attacks and nucleophilic
reaction for the study of biological recognition process [64] and
hydrogen bonding interactions [65]. In order to predict the molecu-
lar reactive sites, the MEP for the title compound is calculated at
B3LYP method as shown in Fig. 7. The different values of the electro-
static potential at the surface are represented by different colors. Po-
tential increases in the order red < orange < yellow < green < blue
where blue indicates the highest electrostatic potential energy and
red indicates the lowest electrostatic potential energy. Intermediary
colors represent intermediary electrostatic potentials. As it can be
seen from the MEP map of the title compound, the both carbonyl
groups have the lowest value of electrostatic potential energy. The
charge of the oxygen atoms in the carbonyl group is ꢂ0.863 e which
support the above finding.
Fig. 6. In the title compound, the HOMO of
p nature is delocalized
over the whole CAC bonds of the phenyl ring, and CO groups and
LUMO is mainly on the anhydride group. Accordingly the HOMO–
LUMO transition implies an electron density transfer from the
phenyl ring to the CO through the CC group. For understanding
various aspects of pharmacological sciences including drug design
and the possible eco-toxicological characteristics of the drug mol-
ecules, several new chemical reactivity descriptors have been pro-
posed. Conceptual DFT based descriptors have helped in many
ways to understand the structure of the molecules and their reac-
tivity by calculating the chemical potential, global hardness and
electrophilicity. Using HOMO and LUMO orbital energies, the ion-
ization energy and electron affinity can be expressed as:
I = ꢂEHOMO, A = ꢂELUMO
,
g
= (ꢂEHOMO + ELUMO)/2 and
l = (EHOMO +
E
LUMO)/2 [61]. Parr et al. [62] proposed the global electrophilicity

Y. Sheena Mary et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 128 (2014) 638–646
645
sponding TMS shielding:
the same theoretical level. Numerical values of chemical shift
calc (TMS) ꢂ calc together with calculated values of
TMS), are reported in Table 3. It could be seen from Table 3 that
rcalc (TMS) is calculated in advance at
d
pred
=
r
r
r
calc
(
1
chemical shift was in agreement with the experimental H NMR
data. Thus, the results showed that the predicted proton chemical
shifts were in good agreement with the experimental data for the
title compound. The protons of phenyl rings resonate in the range
7
.4401–7.9371 theoretically and 7.43–7.86 ppm experimentally.
The circulation of the double bond electrons generate a secondary
magnetic field that accounts for the formation of the magnetic
anisotropy. Therefore, chemical shifts of the hydrogen atoms of
anhydride group are observed at 7.59 (H32, H35) and 6.53 (H33
,
Fig. 7. MEP plot of (2E)-3-phenylprop-2-enoic anhydride.
H34) ppm. The H33 and H34 have been attached with carbonyl
group, therefore electron withdrawing (C@O) group can be de-
creases the shielding and move the resonance of attached proton
towards a higher frequency. In this study, the chemical shifts ob-
tained and calculated for the hydrogen atoms groups are quite low.
Geometrical parameters
The optimized geometrical parameters are given in Table S3 as
Supporting material, atom labeling according to Fig. S2 (Supporting
material). For the title compound, the CAC bond lengths in benzene
rings is between 1.3881 and 1.4049 Å, which is much shorter than
the typical CAC single bond (1.54 Å) and longer than the C@C double
Conclusion
The vibrational properties of (2E)-3-phenylprop-2-enoic anhy-
dride have been investigated using experimental techniques
(FT-IR and FT-Raman) and density functional theory employing
B3LYP exchange correlation. The theoretically vibrational wave-
numbers were compared with the experimental values, which
yield good agreement with the calculated values. The complete
assignments of fundamental modes were performed on the basis
of potential energy distribution. The magnetic properties of the ti-
tle compound are observed and calculated using GIAO procedure,
which is somewhat superior since it exhibits a faster convergence
of the calculated properties upon the extension of the basis set
3
bond (1.34 Å) [66]. The bond length of CAC (C26AC20 and C AC12)
which connects the benzene rings with the anhydride group is of
the order of 1.4613 Å which clearly shows the typical single bond
character and the elongation is due to the presence of the adjacent
groups. In the present case the C@C bond length is 1.3442 Å which
is in agreement with the value given by Nie et al. [66]. The C@O bond
length (1.1989 Å) given by DFT calculation agree with the reported
literature values [38]. With respect of carbonyl group, the maximum
bond angles are 127.5° (C19AC17AO18 and C13AC14AO15). Mean-
while the other angles O16AC17AC19 and O16AC14AC13 shared 360°
with compensation of 109.6° in the carbonyl group. The bond angle
1
used. H NMR chemical shifts are compared with experimental
C
17AO16AC14 is 121.4° which is agreement with reported literature
39]. At the positions C26 and C the bond angles C21AC26
AC25 = 118.2°, C21AC26AC20 = 118.6°, C25AC26AC20 = 123.2°, C AC
AC12 = 123.2°, C AC AC12 = 118.6° and C AC AC = 118.2°. The
data and show a good agreement. The out-of-plane CH deforma-
ꢂ1
[
3
tion at 757 cm
and the out-of-plane ring deformation at
ꢂ1
691 cm in the IR spectrum form a pair of strong bands character-
istics of mono substituted benzene derivatives. The NBO analysis
shows strong intermolecular hyper conjugative interaction of
2
3
4
3
2
3
4
reduction in the phenyl ring angles is due to the presence of the adja-
cent groups.
p-electrons in the molecule leading to stabilization of the mole-
cule. As it can be seen from the molecular electrostatic potential
map of the title compound, the both carbonyl groups have the low-
est value of electrostatic potential energy. In the title compound,
1
H NMR spectrum
the HOMO of
p nature is delocalized over the whole CAC bonds
The experimental spectrum data of the title compound in DMSO
with TMS as internal standard is obtained at 400 MHz and is dis-
played in Table 3. The 1H NMR spectrum is given as Supporting
material (Fig. S3). The absolute isotropic chemical shielding of
the title compound was calculated by B3LYP/GIAO model [67].
Relative chemical shifts were then estimated by using the corre-
of the phenyl ring, and CO groups. The calculated first hyperpolar-
ꢂ30
izability of the title compound is 12 ꢁ 10
esu, and is 92.31 times
that of the standard NLO material urea and the title compound is
an attractive object for future studies of nonlinear optical proper-
ties. Quantum chemical parameters were arrived from the frontier
molecular orbital theory.
Table 3
Acknowledgments
Experimental and calculated 1H NMR parameters (with respect to TMS).
A.A. Al-Saadi thanks King Fahd University for Petroleum & Min-
erals (KFUPM) for providing the computing facility to support this
work. The authors are thankful to University of Antwerp for access
to the University’s CalcUA Supercomputer Cluster.
Proton
r
TMS
r
calc
d
calc
(
r
TMS ꢂ
r
calc
)
Exp. dppm
7
8
9
1
1
2
2
2
3
3
3
3
3
3
H
H
H
32.7711
25.3310
24.8340
25.2412
25.2373
25.2971
25.2413
25.2373
25.2971
25.3310
24.8340
24.9962
25.9106
25.9106
24.9962
7.4401
7.9371
7.5299
7.5338
7.474
7.5298
7.5338
7.474
7.4401
7.9371
7.7749
6.8605
6.8605
7.7749
7.43
7.86
7.45
7.57
7.44
7.45
7.57
7.44
7.43
7.86
7.59
6.53
6.53
7.59
–
–
–
–
–
–
–
–
–
–
–
–
–
0H
1H
7H
8H
9H
0H
1H
2H
3H
4H
5H
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2014.02.194.
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