Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

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

Spectroscopic investigation (FTIR spectrum), NBO, HOMOLUMO

energies, NLO and thermodynamic properties of 8-Methyl-N-vanillyl-6nonenamideby DFT methods
J. Sherin Percy Prema Leela a, R. Hemamalini b, S. Muthu c,, Abdulaziz A. Al-Saadi d
a

Department of Electronic Science, JBAS College for Women, Tamilnadu, India

PG & Research Department of Physics, Queen Marys College, Tamilnadu, India
Department of Physics, Sri Venkateswara College of Engineering, Sriperumpudur 602105, Tamilnadu, India
d
Department of Chemistry, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
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 complete vibrational assignment

In this work, the complete vibrational assignment with PED of 8-Methyl-N-vanillyl-6-nonenamide were
calculated using density functional theory (DFT) based on scaled quantum chemical approach. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Comparison of
simulated spectra with the experimental spectra provides important information about the ability of
the computational method to describe the vibrational modes.

and PED calculations have been done.

 Thermodynamic properties were
determined at different temperatures.
 HOMOLUMO energies, MEP
distribution of the molecule were
calculated.
 NLO and NBO analysis of the
molecule were calculated.

a r t i c l e

i n f o

Article history:
Received 8 November 2014
Received in revised form 23 January 2015
Accepted 1 March 2015
Available online 9 March 2015
Keywords:
FT-IR
DFT
NBO
NLO

a b s t r a c t
Capsicum a hill grown vegetable is also known as red pepper or chili pepper. Capsaicin(8-Methyl-Nvanillyl-6-nonenamide) is the active component in chili peppers, which is currently used in the treatment
of osteoarthritis, psoriasis and cancer. Fourier transform infrared (FT-IR) spectrum of Capsaicin in the
solid phase were recorded in the region 4000400 cm1 and analyzed. The vibrational frequencies of
the title compound were obtained theoretically by DFT/B3LYP calculations employing the standard
6-311++G(d,p) basis set and were compared with Fourier transform infrared spectrum. Complete
vibrational assignment analysis and correlation of the fundamental modes for the title compound were
carried out. The vibrational harmonic frequencies were scaled using scale factor, yielding a good
agreement between the experimentally recorded and the theoretically calculated values. Stability of
the molecule arising from hyper conjugative interactions, charge delocalization and intra molecular
hydrogen bond-like weak interaction has been analyzed using Natural bond orbital (NBO) analysis by
using B3LYP/6-311++G(d,p) method. The results show that electron density (ED) in the r and p
antibonding orbitals and second-order delocalization energies E (2) conrm the occurrence of intra
molecular charge transfer (ICT) within the molecule. The dipole moment (l), polarizability (a) and the

Corresponding author. Tel.: +91 9443690138.

E-mail addresses: mutgee@gmail.com, muthu@svce.ac.in (S. Muthu).
http://dx.doi.org/10.1016/j.saa.2015.03.027
1386-1425/ 2015 Elsevier B.V. All rights reserved.

178

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

hyperpolarizability (b) values of the molecule has been computed. Thermodynamic properties (heat
capacity, entropy and enthalpy) of the title compound at different temperatures were calculated.
2015 Elsevier B.V. All rights reserved.

Introduction
Capsicum is the name of a group of annual plants in the
Solanaceae family. They are native to Mexico and Central
America but are cultivated for food in many warmer regions of
the world. Capsicum varieties include the cayenne pepper,
jalapeno pepper, other hot peppers, and paprika. Capsaicin is the
most-studied active ingredient in the plant and has been approved
by the U.S. Food and Drug Administration (FDA) for use on the
skin. Capsaicin (8-Methyl-N-vanillyl-6-nonenamide) is an active
component [1] of chili peppers, which are plants belonging to the
genus Capsicum. It is an irritant for mammals, including human
beings, and produces a sensation of burning in any tissue with
which it comes into contact. Pure capsaicin is a volatile, hydrophobic, colorless, odourless, waxy compound. The molecular formula
for 8-Methyl-N-vanillyl-6-nonenamide is C18H27NO3 and its
molecular mass is 305.41 g mol1. The compound [2] was rst
extracted in 1816 by Christian Friedrich Bucholz. Capsaicin is
present in large quantities in the placental tissue which holds the
seeds, the internal membranes and, to a lesser extent, the other
eshy parts of the fruits of plants in the genus Capsicum. The seeds
themselves do not produce any capsaicin, although the highest
concentration of capsaicin can be found in the white pith of the
inner wall, where the seeds are attached [2]. Capsaicin has
analgesic and anti-inammatory activities and is used currently
in creams and gels (e.g., Axsain and Zostrix) to mitigate neurogenic
pain. The drug purportedly reduces pain caused by osteoarthritis
[3], joint and/or muscle pain from bromyalgia and from other
causes. One study with human subjects indicates that capsaicin
may be used to help regulate blood sugar levels by affecting
carbohydrate breakdown after a meal [4]. Capsaicin creams are
used to treat psoriasis and reduce itching and inammation [5].
Medical researchers are now looking at the use of capsaicin as a
potential for cancer treatment. Capsaicin has been shown to slow
the growth of prostate cancer cells in laboratory studies and
rodents. Researchers are looking into the use of capsaicin for
prostate cancer in humans. Even though a treatment may look
promising in animal and laboratory studies, further studies are
required to nd out whether the results apply to humans. Due to
the above biological importance of our compound, we have
evinced keen interest to report a conclusive conformational and
vibrational study with the help of Density functional theory
calculations as well as infrared techniques.
In recent years, among the computational methods calculating
the electronic structure of molecular systems, DFT methods has
been a favorite one due to its great accuracy in reproducing the
experimental values of molecular geometry, vibrational frequencies, atomic charges, dipole moment, thermo dynamical properties,
etc [613]. A literature survey reveals that to the best of our knowledge no HF/DFT wave number and structural parameter calculation
of 8-Methyl-N-vanillyl-6-nonenamide has been reported so far.
This inadequacy observed in the literature encouraged us to carry
out theoretical and experimental vibrational spectroscopic
research on the molecule to give a correct assignment of the
fundamental bands in experimental FT-IR spectrum on the basis
of calculated Potential energy distribution (PED). Therefore, the
present study aims to give a complete description of the molecular
geometry, molecular vibrations and electronic features of the
present molecule. The redistribution of electron density (ED) in

various bonding, anti bonding orbital and E2 energies have been

calculated by natural bond orbital (NBO) analysis to give clear
evidence of stabilization originating from the hyper conjugation
of various intramolecular interactions. The HOMO, LUMO analysis
has been used to elucidate information regarding charge transfer
within the molecule. In addition, MEP (Molecular electrostatic
potential) and thermodynamic properties were also calculated.
The rst order hyperpolarizability (btotal) of this molecular system
and related properties (b, l, and Da) are calculated using B3LYP/
6-311++G(d,p)methods based on the nite-eld approach. All the
calculations were performed using the Gaussian 03 program [14].
Computational details
In the present paper, density functional theory was adopted by
employing B3LYP/6-311++G(d,p) basis set level to calculate the
properties of the title molecule. The calculations were performed
with the Gaussian 03W program package, invoking gradient
geometry optimization [15] using Pentium IV personal computer.
The vibrational frequencies for this molecule were calculated with
the B3LYP method with 6-311++G(d,p) basis set and then scaled
[16] by 0.967. The vibrational wave number assignments and
PED calculation have been carried out by combining the results
of the Gauss View and the VEDA program [17,18] with symmetry
considerations. The Natural Bonding Orbital (NBO) calculation
was performed using NBO 3.1 program [15] and was carried out
in the Gaussian 03W package at the DFT/B3LYP level. The hyper
conjugative interaction energy was deducted from the second
order perturbation approach [1921]. HOMO and LUMO analysis
have been used to elucidate the information regarding charge
transfer within the molecule and Molecular electrostatic potential
analysis has been used to nd the reactive sites of the compound in
the Gaussian 03W package at the DFT/B3LYP level.
Experimental
The placental tissue of the capsicum was dried, powdered and
taken in a lter paper. This was placed inside the condenser of a
sterile round ask containing ethanol which acts as a solvent.
The contents were heated and maintained at a constant temperature of 5560 C for 35 h. The evaporated capsaicin was collected
on the walls of the tube. The process was repeated three to four
times and the extract was collected and dried. The FT-IR spectrum
of the freshly prepared capsaicin (8-Methyl-N-vanillyl-6-nonenamide) belonging to C1 point group symmetry was recorded in
the region 4000400 cm1, using Bruker IFS 66V Spectrometer.
Fig. 1 shows the recorded FTIR spectrum and the theoretically predicted FTIR spectrum obtained from B3LYP/6-311++G(d,p) level
calculations.
Results and discussion
Vibrational analysis
The title compound consists of 49 atoms and has 141 normal
modes of vibration. The observed and theoretically scaled frequencies along with their PED are presented in Table 1. The functional
groups present in the molecule were identied and a satisfactory

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

179

Fig. 1. Experimental and theoretical FTIR spectra of 8-Methyl-N-vanillyl-6-nonenamide.

vibrational band assignment has been made for the fundamental

modes of vibration by observing the position, shape and intensity
of the bands.

scissoring and CH2 wagging vibration are in close agreement

with recorded FT-IR peaks at 1417 cm1 and 1341 cm1 with a
good PED.

NH stretch
The vibrations belonging to NH stretching [22] always occur in
the region 34503250 cm1. In this study, the FTIR NH stretching
band is observed experimentally at 3309 cm1. The theoretically
calculated values by B3LYP/6-311++G(d,p) method at 3628 cm1
is assigned to NH stretching vibrations. The PED contribution of
these modes is 100%. When proceeding to lower energy, the
observed band at 1513 cm1 are partially coupled to CN and
NH bending deformation and the theoretical value is at
1451 cm1 with poor PED contribution.

CO vibration
The IR absorption is sensitive for both the Carbon and Oxygen
atoms of the carbonyl group. Normally the CO stretching vibrations occur in the region 12601000 cm1 [28]. In the present
study, the CO stretching vibration is assigned at 1186 cm1and
1085 cm1 for the title compound which shows good agreement
with calculated frequencies 1181 cm1and 1088 cm1. The PED
contributions are 11% and 11% respectively.

CH stretching
The Aromatic CH ring stretching vibrations are normally found
in the region 31003000 cm1 [23]. However these bands are
rarely useful because they overlap with one another resulting
in stronger absorption in this region. In the FTIR spectrum the
bands observed at 2927 cm1 and 2857 cm1 are assigned to CH
stretching vibrations. Scaled vibrations assigned to the aromatic
CH stretching are 2928 cm1 and 2874 cm1 with the PED
contribution of 89% and 99% showing good agreement with the
recorded FTIR spectrum. The CH out of plane bending vibrations
occur in the region 1000750 cm1 in aromatic compound
[24,25]. The experimental band at 967 cm1 and 938 cm1 are
assigned as CH out of plane bending and have good matching
with theoretical wave number.

CC vibration
The CarbonCarbon stretching modes are expected in the range
from 16001400 cm1 [29]. The observed frequency 1626, 1596,
1553, 1528 cm1 of FTIR spectrum are assigned as CC stretching
vibrations. Silverstein et al. [30] assigned CN stretching vibrations
in the region 13821266 cm1 for aromatic amines. The CN
stretching bands observed at 1239 cm1 and the theoretically
calculated vibration at 1229 cm1 have good agreement with
PED. The CCC trigonal bending vibrations exhibit the characteristic
frequencies at 995 cm1 and 1010 cm1 respectively [31]. The
experimental frequencies 896 and 806 cm1 are assigned as CCC
in plane bending and the scaled frequencies are 894 and
875 cm1 with PED 29% and 32%. The experimental frequencies
758,715 and 645 cm1 are assigned as CCC out of plane bending
with 26%, 11% and 10% PED contributions.
NBO analysis

CH2 bending vibrations

The CH2 bending modes follow the general order of wave numbers, CH2 deformation > CH2 wagging > CH2 twisting > CH2 rocking.
The bending modes involving Hydrogen atom attached to the
central Carbon falls in the 1450875 cm1 range [26,27]. It is
notable that both CH2 scissoring and CH2 rocking are sensitive to
the molecular conrmation. The scaled vibrational frequencies in
the range from 1431 to 1284 cm1 (mode No. 9882), 1267 cm1
(mode No. 79) and 1071 cm1 (mode No. 63) are assigned to CH2
bending modes. The scaled vibrational frequencies at 1419 cm1
(mode No. 94) and 1346 cm1 (mode No. 88) are assigned to CH2

The natural bond orbital analysis provides an efcient method

for studying intra and inter molecular bonding and interaction
among bonds and also provides convenient basis to investigate
charge transfer or conjugative interaction in molecular systems.
NBO analysis has been performed on 8-Methyl-N-vanillyl-6-nonenamide using NBO 3.1 program [32] in the Gaussian 03w package
at the B3LYP/6-311++G(d,p) level. Natural bond orbital (NBO)
method of weinhold et al. [33] provides a scheme appropriate to
the analysis of lewis acid/base interactions [33,34]. Since these
interactions lead to loss of occupancy from the localized NBOS of

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J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

Table 1
Experimental and calculated DFT-B3LYP/6-311++G(d,p) levels of vibrational frequencies (cm1) of 8-Methyl-N-vanillyl-6-nonenamide.
Mode
Nos.

Experimental wave numbers

(cm)1

Calculated wavenumbers B3LYP/

6311++G(d,p) cm1

FT-IR

137
136
135
134
133
132
131
130
129
128
127
126
125
124
123
122
121
120
119
118
117
116
115
114
113
112
111
110
109
108
107
106
105
104
103
102
101
100
99
98
97
96
95
94
93
92
91
90
89
88
87
86
85
84
83
82
81
80
79
78
77
76
75
74
73
72
71
70
69
68
67
66
65

3620w
3309vs
3073vw
3068w
3028s
3013vw
2987vw

3628
3490
3077
3068
3038
3016
2986
2979
2974
2970
2969
2961
2959
2958
2952
2937
2933
2928
2912
2902
2901
2900
2896
2893
2892
2883
2874
1657
1656
1584
1579
1483
1473
1451
1451
1446
1443
1434
1433
1431
1430
1427
1424
1417
1415
1407
1362
1352
1341
1341
1337
1331
1319
1292
1285
1284
1282
1269
1267
1246
1240
1229
1219
1214
1197
1181
1176
1160
1153
1139
1129
1123
1097

105
20
4
7
12
20
3
59
35
21
24
28
60
46
1
34
0
28
29
33
37
44
28
8
8
21
18
193
5
22
16
197
280
19
2
51
7
1
10
3
0
5
1
16
7
31
3
30
9
3
5
11
21
23
4
1
11
3
1
196
13
50
50
114
5
62
121
23
17
1
48
1
32

2970w
2966vw
2954vw
2948 ms
2936vw
2927s

2899vw

2857 ms
1651s
1626vs
1596s
1553w
1528vw
1513vs
1451 ms

1419s

1346w

1282vs

1258vw

1239s
1201 ms

1174w

1123vw

Relative

Assignments PED
a

Absolute
37
7
1
2
4
7
1
21
12
8
9
10
21
17
0
12
0
10
10
12
13
16
10
3
3
8
6
69
2
8
6
70
100
7
1
18
2
0
3
1
0
2
0
6
2
11
1
11
3
1
2
4
8
8
2
0
4
1
0
70
5
18
18
41
2
22
43
8
6
0
17
0
11

cOH(100)
cNH(100)
cCH(97)
cCH(100)
cCH(99)
cCH(97)
cCH(100)
cCH(100)
cCH(98)
cCH(100)
cCH(86)
cCH(85)
cCH(78)
cCH(99)
cCH(90)
cCH(94)
cCH(98)
cCH(89)
cCH(92)
cCH(96)
cCH(100)
cCH(84)
cCH(86)
cCH(93)
cCH(85)
cCH(90)
cCH(99)
cOC(88)
cCC(82)
cCC(46), bCCC(34)
cCC(60)
cCC(16), cOC(39)
cCC(47), cOC(13)
cNC(57), bHNC(29)
cCC(48), cOC(15), bHOC(20)
cCC(12), cOC(30), bHOC(29)
cCC(57)
cCC(22), bHOC(17), bHCH(51)
cCC(11), sHCCC(23)
bHCH(88)

cNC(23), cCC(12)
bHCH(92)
cCC(28), cOC(22), bHCH(12)
cNC(18), bHNC(24), bHCHsci (12)
bHNC(17), bHCH(43)
bHCH(58)
bHCH (71)
bHCHwag (57)
bHCH(66)
bHCH(84)
bHCH(83)
bHCH(87)
bHCH(62)
cCC(15)
bHCH(74)
bHCH(11), sHCCN(33)
cCC(57), sHCCC(22)
cCC(17), bHCC(13)
bHCH(67), sHCOC(12)
cOC(68), bHCC(58)
bHCC(35), sHCCC(14)
cNCC(22), sHCCC(40)
bHCC(43)
bHCC(42), bHCC(12)
cCC(24), bHCC(19)
bHCC(52), sHCOC(11)
cCC(17)
cCC(11), bHCC(21)
cCC(41), bHCC(10)
bHCC(23)
cCC(31), sHCCC(53)
bHCC(30)
bHCC(33), bHCCC(15)

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

181

Table 1 (continued)
Mode
Nos.
64
63
62
61
60
59
58
57
56
55
54
53
52
51
50
49
48
47
46
45
44
43
42
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1

Experimental wave numbers

(cm)1

1029w

967vw
938vw

896vw
879vw
841vw
806 ms
758vw

715w

645w

Calculated wavenumbers B3LYP/

6311++G(d,p) cm1

FT-IR
Relativea

Assignments PED
Absoluteb

1088
1071
1060
1034
1020
1016
1001
997
985
963
955
923
914
909
902
894
875
859
841
813
808
800
778
754
724
712
701
693
645
598
542
532
515
496
467
456
446
437
434
419
374
360
351
328
306
286
263
252
232
226
217

12
5
2
4
2
44
2
15
2
37
4
0
5
4
2
0
0
25
3
1
0
17
26
3
19
4
7
0
9
17
21
2
1
6
30
18
22
33
4
97
3
1
3
2
6
3
1
2
1
0
0

4
2
1
2
1
16
1
5
1
13
2
0
2
1
1
0
0
9
1
0
0
6
9
1
7
1
2
0
3
6
7
1
1
2
11
6
8
12
1
35
1
0
1
1
2
1
1
1
0
0
0

196
194
179
167
138
129
105
97
92
76
56
48
41

0
0
0
4
4
0
3
2
0
4
8
2
2

0
0
0
2
2
0
1
1
0
1
3
1
1

bHCC(47), sHCOC(11)
bHCH(26), sHCOC(72)
bHCC(25)
bHCC(38)
cCC(16), bHCC(10)
bHCC(23)
bHCC(22)
cCC(34), sHCCC(34)
sHCCC(69)
cCC(18), sHCCC(20)
sHCCC(38)
sHCCC(59), sCCCC(24)
cCC(11), sHCCC(10)
sHCCC(45)
bCCC(11), sHCCC(17)
cOC(10), binbCCC(29)
sHCCC(55), sCCCC(30)
sHCCC(41)
sHCCC(84)
sHCCC(25)
cCC(11), binCCC(32)
bHCC(16), sHCCC(38)
sHCCC(22), bopOCCC(26)
bop OCNC(47)
bNCC(15), bop OCCC(10), CCCC(14)
bOCC(12), bopOCCC(11)
bOCN(32), bCNC(11)
bCCC(42), bopCCCC(10)
bCCC(13), bopCCCC(10)
bCCC(44), bopCCCC(19)
bCCC(10), bopOCC(32)
bOCN(11), bCCN(35)
bCOC(12), bopOCCC(37)
bOCN(12), sHNCC(65)
bCCC(55)
bCCC(48)
bCCC(42)OPCCCC(20)
bCCC(11), bOCC(19), bCOC(29)
sCCCC(22), bopOCCC(14)
bOCC(10), bCCC(23), bCCN(10)
bCCC(25)
bOCC(31)
bNCC(18)
bCCC(51)
sHOCC(81)
bCCC(26)
sHOCC(10), sHCOC(30)
bCNC(16), bOCC(10), bCCC(22)
bCNC(11), bCCC(10), sCCCC(15)
sHCCC(81)
sCCCC(20), bop OCCC(21) bop
CCCC(12)
sHCCC(94)
sCCCC(53), sCCNC(12)
sCCCC(24)
sCCC(50)
sCNCC(23), sCCCC(11)
sCCCC(62)
sCNCC(28), sCOCC(28)
sCOCC(48)
sCCCC(43)
sNCCC(20), sCCNC(29)
sCCCC(18), sNCCC(17), sCCNC(23)
sCCCC(26), sNCCC(25), sCCCC(13)
sCCCC(45), sCCCN(31)

Abbreviations: s strong; vs verystrong; m medium; ms mediumstrong; w weak; vw veryweak; c stretching; b bending; s Torsion, inp plane bending,
opb out of plane bending.
a
Absolute absorption intensity.
b
Relative absorption intensities normalized with highest peak absorption equal to 100.

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Table 2
Second order perturbation theory analysis of fock matrix of 8-Methyl-N-vanillyl-6-nonenamide in NBO basis B3LYP/6-311++G(d,p) method.
Donor (i)

a
b
c

Type

ED/e

C1C2

1.96891

C1C6

1.97578

C1C6

1.97578
1.69482

C1H26

1.97446

C2C3

1.97377

C2C3

1.69197

C3C4

1.97398

C3H27

1.97954

C4C5
C4C5

r
p

1.97405
1.66814

C4H28

1.97809

C5C6

1.97085

O7H29
C9H33
C10H36
C10H37
N11H40

r
r
r
r
r

1.98651
1.99125

C12C14
C14H38
C14H39
C17C18
C17H45
C17H46

r
r
r
r
r
r

1.97763
1.9794
1.96508
1.97952
1.97882
1.96942

C19C20

1.97415

C19H48
C20H49
C20H49
C20H49
O7
O8
N11
O13
O13

r
r
r
r

1.97273
1.96824
1.96824
1.96824
1.87397
1.86269
1.70607
1.70607
1.70607

LP(2)
LP(2)
LP(1)
LP(2)
LP(2)

1.98073
1.98608

Acceptor (j)
C1C6
C2C3
C6O8
C1C2
C2C10
C5C6
C5O7
C2C3
C4C5
C2C3
C5C6
C1C2
C3C4
C1C6
C4C5
C10N11
C2C3
C2C10
C5O7
C1C2
C4C5
C5C6
C1C6
C2C3
C2C3
C5C6
C1C6
C4C5
O8C9
C4C5
C6O8
N11C12
C2C3
C12O13
C12O13
C10N11
C12O13
C12O13
C19C20
C18H47
C18C19
C17H46
C17C18
C18C19
C18H47
C19H48
C21H32
C22H25
C4C5
C1C6
C12C13
N11C12
C12C14

Type

r
r
r
r
r
r
r
p
p
r
r
r
r
p
p
r
r
r
r
r
r
r
p
p
r
r
r
r
r
r
r
r
r
r
p
r
r
p
r
r
p
r
r
r
r
r
r
r
p
p
p
r
r

ED/e

a (2)

0.02481
0.02386
0.02862
0.02236
0.02989
0.03630
0.02009
0.37525
0.37907
0.02386
0.03630
0.02236
0.01227
0.38685
0.37907
0.03227
0.02386
0.02989
0.02009
0.02236
0.02132
0.03630
0.38685
0.37525
0.02386
0.03630
0.02481
0.02132
0.00967
0.02132
0.02862
0.07379
0.02386
0.03371
0.26947
0.03227
0.03371
0.26947
0.02335
0.02317
0.05091
0.01912
0.01461
0.01262
0.02317
0.02419
0.00867
0.00867
0.37907
0.38685
0.26947
0.07379
0.06053

3.39
3.58
4.78
3.61
3.27
4.36
3.11
18.8
19.17
4.51
3.89
3.55
3.13
19.49
19.05
4.67
3.48
3.79
4.17
4.79
3.16
3.79
18.88
20.32
3.47
3.99
4.14
3.89
3.36
4.73
3.33
3.29
4.03
4.2
0.51
4.28
4.11
4.64
3.73
4.25
3.85
3.02
3.67
3.06
5.78
4.63
2.96
2.97
27.39
25.43
51.64
24.25
19.03

(kJ/mol)

1.26
1.28
1.03
1.3
1.13
1.26
1.07
0.3
0.29
1.11
1.06
1.28
1.28
0.28
0.28
0.58
1.28
1.1
1.05
1.1
1.09
1.25
0.29
0.3
1.1
1.06
1.28
1.28
0.98
1.31
0.88
0.98
1.1
1.24
0.73
0.97
1.07
0.56
1.06
0.92
0.55
0.66
1.05
1.31
0.94
0.91
0.88
0.88
0.35
0.36
0.32
0.72
0.63

0.059
0.061
0.063
0.061
0.054
0.066
0.052
0.069
0.068
0.063
0.058
0.06
0.057
0.067
0.066
0.05
0.06
0.058
0.059
0.065
0.052
0.062
0.066
0.07
0.055
0.058
0.065
0.063
0.052
0.07
0.049
0.052
0.06
0.065
0.018
0.058
0.059
0.048
0.056
0.056
0.041
0.04
0.056
0.057
0.066
0.058
0.046
0.046
0.093
0.091
0.115
0.119
0.1

E(j)  E(i) (a.u)

F(i,j) (a.u)

E(2) means energy of hyper conjugative interaction (stabilization energy).

Energy difference between donor and acceptor i and j NBO orbitals.
F(i, j) is the Fock matrix element between i and j NBO orbitals.

the idealized lewis structure into the empty non lewis orbitals,
they are referred to as delocalization correction to the Zeroth
Order natural Lewis structure. For each donor (i) and acceptor (j),
the stabilization energy E(2) associated with the delocalization
i ? j is estimated as:

E2 DEij

qi F ij 2
ej  ei

where qi is the donor orbital occupancy, ej and ei are diagonal

elements and Fij is the off diagonal NBO Fock matrix element. The
larger E(2) value, the more intensive is the interaction between electron donors and acceptors, i.e., the more donation tendency from
electron donors to electron acceptors and the greater the extent

of conjugation of the whole system. The intra molecular hyper

conjugative interactions are formed by orbital overlaps between r
and p (CC, CN, C@O, CH, NH) bond orbitals which results
intra-molecular charge transfer (ICT) causing stabilization of the
system. These interactions are observed as increase in electron
density (ED) in CC, CH, CO and NH antibonding orbital that
weakens the respective bonds. Delocalization of electron density
between occupied Lewis-type (bond or lone pair) NBO orbital and
formally unoccupied (antibond or Rydgberg) non-Lewis NBO orbital
correspond to a stabilizing donoracceptor interaction. The strong
intramolecular hyper conjugative interaction of the r and p
electrons of CC to the antibond CC bond in the ring leads to
stabilization of some part of the ring as evident from Table 2. For
example the intramolecular hyper conjugative interaction of

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

183

(C1C6) distribute to r (C1C2), r (C2C10), r (C5C6), r (C5O7)

leading to stabilization of 4.36 kJ/mol. This enhanced conjugation
with bonding orbital of p (C1C6) distribute to p (C2C3), p (C4C5)
which leads to strong delocalization of 18.8 and 19.17 kJ/mol
respectively. In case of the orbitalr (N11H40) distribute to r
(C12O13), p (C12O13), with the stabilization energy of
4.2 kJ/mol. The most important interaction energy in this molecule
is electron donating from N11 LP(1) to the antibonding acceptor p
(C12C13) resulting high stabilization energy of 51.64 kJ/mol.
Therefore, the maximum energy delocalization takes place in the
pp transition.
Potential energy surface (PES) scan
The optimized conformers of the molecule 8-Methyl-N-vanillyl6-nonenamide is obtained from Gaussian 03W program and is
shown in Fig. 2, with calculated energies for C1 point group
symmetry. The conformational prole of the title compound has
been investigated at the B3LYP/6-311++G(d,p) level. The multirotor nature of the compound and the absence of an experimental
data that elucidate its chemical structure required us to carry out a
detailed investigation of the conformationality and energetic to
locate the global minima. The E congurations were calculated to
be about 1.5 kcal/mol more stable than the Z congurations.
Moreover, for the E conguration, the syn structure (the CH2
groups at C15 is syn to the carbonyl group) was also calculated to
be 1 kcal/mol more stable than the anti structure. The determination of the most stable E-syn form hasbeen conrmed by
screening the energy change when the phenyl group is rotated
about the C10N11 bond. Again, two possible E-syn forms, I and
II, are theoretically present are shown in the Fig. 3. Structure II
is 1 kcal/mol more stable and maintains a CC10N11C dihedral
angle of 92 are shown in the Table S1. Structure I is shown by
the potential scan to have a at minima and expected to be easily
stable. For the anti conguration, this at minima couldnt be
located. One feature of the stable structures is the intramolecular
hydrogen bonding taking place between O8 and H29. The bonding,
estimated to be 2.1 , is expected to provide an extra stability to
the molecule in the order of 5 kcal/mol [35,36].
Molecular electrostatic potential
The electrostatic potential V(r) that is created in the space
around a molecule by its nuclei and electrons (treated as static
distributions of charge) is a very useful property for analyzing
and predicting molecular reactive behavior. It is rigorously dened
and can be determined experimentally as well as computationally.
The molecular electrostatic potential is related to electron density

Fig. 2. The most stable conguration (E-syn) of 8-Methyl-N-vanillyl-6-nonenamide

as predicted by the B3LYP/6-311++G(d,p) level.

Fig. 3. Potential energy scan for the internal rotation about the C10N11 bond in
8-Methyl-N-vanillyl-6-nonenamide calculated at the B3LYP/6-311++G(d,p) level of
theory.

and a very useful descriptor for determining sites for electrophilic

attack and nucleophilic reactions as well as hydrogen-bonding
interactions [35,36]. To predict reactive sites of electrophilic
and nucleophilic attacks for the investigated molecule 8-MethylN-vanillyl-6-nonenamide, MEP at the B3LYP level optimized
geometry with the basis set 6-311++G(d,p) was calculated and
shown in the Fig. 4. The different values of the electrostatic potential at the MEP surface are depicted by different colours red, blue
and green representing the regions of most negative, most positive
and zero electrostatic potential respectively. The negative electrostatic potential corresponds to an attraction of the proton by the
aggregate electron density in the molecule (shades of red), while
the positive electrostatic potential corresponds to the repulsion
of the proton by the atomic nuclei (shade of blue). The negative
(red and yellow) regions of MEP were related to electrophilic
reactivity and the positive (blue) regions to nucleophilic reactivity.
From the MEP it is evident that the negative potential sites are on
electronegative Oxygen atoms and the positive potential sites are
around the Hydrogen atoms.
Frontier molecular orbitals (FMOs)
The (HOMO) highest occupied molecular orbital and the
(LUMO) lowest unoccupied molecular orbital are named as frontier
molecular orbitals (FMOs) as they lie at the outermost boundaries
of the electrons of the molecules. The FMOs play an important role
in the optical and electric properties, as well as in quantum
chemistry and UVVis spectrum [37]. The HOMO represents the
ability to donate an electron, LUMO as an electron acceptor represents the ability to accept an electron. The energies of HOMO and
LUMO orbitals of the compound in gas phase are 5.9365 and
0.4893 eV respectively. The HOMO and LUMO orbital energy gap
calculated using B3LYP/6-311++G(d,p) method is +5.4472 eV. The
positive and negative phase represented in red and blue colour,
respectively are shown in Fig. 5. The Frontier orbital gap helps
characterize the chemical reactivity and the kinetic stability
of the molecule. A molecule with a small frontier orbital gap is
generally associated with a high chemical reactivity, low kinetic
stability and is also termed as soft molecule. The lower value
of HOMO and LUMO energy gap explains the eventual charge
transfer interactions taking place within the 8-Methyl-N-vanillyl6-nonenamide molecule.

184

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

Fig. 4. Electro static potential with contour (ESP), molecular electrostatic potential (MEP) and contour map of 8-Methyl-N-vanillyl-6-nonenamide obtained by
B3LYP/6-31++G(d,p) method.

LUMO PLOT
First exited
E(LUMO)= -0.4893 eV

LUMO

E = 5.4472 eV

E(HUMO)= -5.9364eV

HOMO PLOT
Ground state
HOMO
Fig. 5. Highest occupied and lowest unoccupied molecular orbitals of 8-Methyl-N-vanillyl-6-nonenamide compound obtained by B3LYP/6-31+G(d,p) method.

Non linear optics

Non linear optical (NLO) [3840] effects are analyzed by
considering the response of the dielectric material at the atomic
level to the electric elds of an intense light beam. The propagation

of a wave through a material produces changes in the spatial and

temporal distribution of electrical charges as the electrons and
atoms interact with the electromagnetic elds of the wave. The
main effect of the forces exerted by the eld on the charged
particles is displacement of the valence electrons from their

J. Sherin Percy Prema Leela et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 146 (2015) 177186

normal orbits. This perturbation creates electric dipoles whose

macroscopic manifestation is the polarization [41]. Thus Nonlinear
optics (NLO) is the study of interaction of intense electromagnetic
eld with materials to produce modied elds that are different
from the input eld in phase, frequency or amplitude. Nonlinear
optics [42,43] is given increasing attention due to its wide application in the area of laser technology, optical communication and
data storage technology. The second-order polarizability or rst
hyperpolarizability b, dipole moment l and polarizability Da of
the Capsaicin compound are calculated using B3LYP 6-31G(d,p)
basis set on the basis of the nite-eld approach. The complete
equations for calculating the magnitude of total static dipole
moment l, the mean polarizability a, the anisotropy of the
polarizability Da and the mean rst polarizability b, using the x,
y, z components from Gaussian 03 W output is as follows:
1=2

ltot l2x l2y l2z

a 1=3axx ayy azz
1=2

Da 21=2 axx  ayy 2 ayy  azz 2 azz  axx 2 6a2xx 

bltot lx ly lz and
bx bxxx bxyy bxzz
by byyy bxxy byzz
bz bzzz bxxz byyz

The calculated dipole moment, polarizability and rst order

hyperpolarizability values obtained from B3LYP/6-311++G(d,p)
method are given in Table S2. Urea is one of the prototypical
molecules used in the study of the NLO properties of molecular
systems and frequently used as a threshold value for comparative
purposes. The rst order hyperpolarizability of Capsaicin is
3.4966  1030 esu which is nine times greater than the value of
urea (b0 = 0.372  1030 esu). So we conclude that the compound
is an attractive object for future studies of nonlinear optical
properties.
4.7. Thermodynamic properties
The thermodynamic parameters namely heat capacity, entropy
and enthalpy of the compounds have also been computed at the
DFT-B3LYP level using 6-311++G(d,p) basis sets at 298.15 K in
ground state and listed in Table S3. The thermodynamic data
provide helpful information for further study on the title
compound. The standard thermodynamic functions can be used
as reference thermodynamic values to calculate the changes of
entropies (DS), changes of enthalpies (DH) and changes of Heat
capacity (DC) of the reaction. The dipole moment and its principal
inertial axes strongly depend upon the molecular conformation.
From Table S3, 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 [4458].
The correlation equations between heat capacities, entropies,
enthalpy changes and temperatures were tted by quadratic
formulas, and the corresponding tting factors (R2) for these
thermodynamic properties are 0.99991, 0.99934 and 0.99991,
respectively.
ENTROPY
S = 315.66926 + 1.54034 T  3.43167  104 T2 (R2 = 0.99991)
HEAT CAPACITY
C = 36.10096 + 1.3561 T  5.01694  104 T2 (R2 = 0.99934)
ENTHALPY
H = 13.70614 + 0.16083 T + 4.06098  104 T2 (R2 = 0.99991)
The correlation graphs between heat capacities, entropies,
enthalpy changes and temperatures were shown in Fig. S1. All

185

the thermodynamic data supply helpful information for the further

study on the Capsaicin compound. The thermodynamic calculations were done in gas phase and they could not be used in
solution.
Conclusions
The use of herbs as complementary and alternative medicine
has increased dramatically in the last 2025 years. Capsaicin the
major pungent ingredient in genus Capsicum, has long been used
in food additives and drugs. An infrared spectrum represents a
nger print of a sample with absorption peaks which correspond
to the frequencies of vibrations between the bonds of the atoms
making up the material. An attempt has been made in the present
work for the proper wave number assignments from FT-IR
spectrum. The vibrational band assignments of the recorded FTIR
spectrum of the molecule (8-Methyl-N-vanillyl-6-nonenamide)
have been compared with the theoretical spectrum and have been
found to be in very good agreement. In PES the most stable
conformer is for 92 dihedral angle is conrmed. The stability of
the molecule arising from hyper conjugative interactions, charge
delocalization has been analyzed using NBO analysis. HOMO
and LUMO energy gaps explain the eventual charge transfer
interactions taking place within the molecule. The rst order
hyperpolarizability of Capsaicin is 3.4966  1030 esu which is
nine times greater than the value of urea (b0 = 0.372  1030 esu)
and polarizability is 3.101  1023 esu.
The thermodynamic functions of capsaicin are increasing
with temperature ranging from 100 K to 1000 K due to the fact
that the molecular vibrational intensities increase with temperature. Other molecular properties like entropy, enthalpy and heat
capacity also calculated. The MEP map shows that the negative
potential sites are on oxygen and the positive potential sites are
around the hydrogen atoms. These sites may provide information
about the possible reaction regions for the title structure. In conclusion, all the calculated data and simulations not only show
the way to the characterization of the molecule but also help for
the fundamental researches in chemistry and biology in the future.
Acknowledgement
A.A. Al-Saadi thanks King Fahd University for Petroleum &
Minerals (KFUPM) for providing the computing facility to support
this work.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2015.03.027.
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