Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320

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Spectrochimica Acta Part A: Molecular and

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

Molecular structure analysis and spectroscopic characterization

of 5-ethyl-5-phenyl-1,3-diazinane-4,6-dione with experimental
(FT-IR and FT-Raman) techniques and quantum chemical calculations
E. Isac Paulraj a,b,⇑, S. Muthu c
a
Research scholar, Manonmaniam Sundaranar University, Tirunelveli 627 012, Tamil Nadu, India
b
Department of Applied Physics, Pallavan College of Engineering, Kancheepuram 631 502, Tamil Nadu, India
c
Department of Applied Physics, Sri Venkateswara College of Engineering, Sriperumbudur 602 105, Tamil Nadu, 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

" FT-IR and FT-Raman spectra of A complete vibrational analysis of 5-ethyl-5-phenyl-1,3-diazinane-4,6-dione is performed by combining
5-ethyl-5-phenyl-1,3-diazinane the experimental and theoretical information using Pulay’s density functional theory (DFT) based on
-4,6-dione in the solid phase were scaled quantum chemical approach. The calculated HOMO and LUMO energies show that charge transfer
recorded and analyzed. occur within the molecule. Comparison of simulated spectra with the experimental spectra provides
" The optimized geometry and important information about the ability of the computational method to describe the vibrational modes.
vibrational wavenumbers were
computed using ab initio HF and DFT
methods.
" The complete vibrational assignment
and spectroscopic analysis have
been carried out.
" The first order hyperpolarizability
and HOMO, LUMO energy gap were
theoretically predicted.
" The NBO analysis explained the
intramolecular hydrogen bonding.

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

Article history: In this work, the FT-IR and FT-Raman spectra of 5-ethyl-5-phenyl-1,3-diazinane-4,6-dione have been
Received 24 July 2012 recorded. The optimum molecular geometry, normal mode wavenumbers, infrared and Raman intensi-
Received in revised form 16 January 2013 ties, Raman scattering activities, corresponding vibrational assignments and Mullikan atomic charges
Available online 1 February 2013
were investigated with the help of HF and B3LYP(DFT) methods using 6-31G(d,p) basis set. The assign-
ments of vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA)
Keywords: following the scaled quantum mechanical force field (SQMFF) methodology. The stability of molecule
HF
has been analyzed by NBO analysis. The calculated HOMO and LUMO energies show that charge transfer
DFT
NBO
interactions take place within the molecule. Finally, the Mulliken population analysis on atomic charges
MEP of the title compound has been calculated.
HOMO–LUMO Ó 2013 Elsevier B.V. All rights reserved.

⇑ Corresponding author at: Research scholar, Manonmanium Sundaranar University, Tirunelveli 627 012, Tamil Nadu, India. Tel.: +91 9442721543.
E-mail address: isacpaulraj@hotmail.com (E. Isac Paulraj).

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.01.048
 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320 311

Introduction frequencies and the experimentally measured frequencies. In this

investigation we observe that the calculated frequencies were
Generic name for 5-ethyl-5-phenyl-1,3-diazinane-4,6-dione is slightly deviate from the fundamental frequencies. To improve
Primidone. It is a derivative of barbituric acid. It is used to control the agreement between the predicted and observed frequencies,
the grand mal seizures, psychomotor, and focal epileptic seizures. the computed harmonic frequencies are usually scaled for compar-
It is a valuable alternative to propranolol in the treatment of ison. For this purpose the scaling of the force field was performed
essential tremor. Unlike many other anticonvulsants, 5-ethyl-5- according to the SQMFF procedure [9], the Cartesian representation
phenyl-1,3-diazinane-4,6-dione (EPDD) works via interactions of the force constants were transferred to a non-redundant set of
with voltage-gated sodium channels which inhibit high-frequency local symmetry coordinates, chosen in accordance to the recom-
repetitive firing of action potentials. Molecular formula for 5-ethyl- mendations of Pulay et al. [10]. The descriptions of the predicted
5-phenyl-1,3-diazinane-4,6-dione (EPDD) is C12H14N2O2. It is a frequencies during the scaling process were followed by the poten-
white powder and soluble in water. Experimental study of tial energy distribution (PED) matrix. The characterization of the
Morphological and cytogenetic effects of hydantoin and primidone normal modes using potential energy distribution (PED) was done
has been carried out [1]. The isolation, identification, and quantita- with the MOLVIB-7.0 program written by Sundius [11,12]. The NBO
tion of a Primidone Metabolite were studied in detail [2]. The calculations [13] were performed using NBO 3.1 program as carried
detailed crystal structure of Primidone [3,4] was reported previ- out in the Gaussian 03W [7] package at the DFT/B3LYP level to
ously. Literature survey reveals that so far there is no complete understand the intramolecular delocalization or hyperconjugation.
theoretical study for the title compound EPDD. In this work, we
mainly focused on the detailed spectral assignments based on The prediction of Raman intensities
the experimental Fourier transform infrared (FT-IR) and Fourier
transform Raman (FT-Raman) spectra as well as DFT/B3LYP The Raman scattering activities (Si) are calculated with Gaussian
calculations for EPDD. The redistribution of electron density (ED) 03W program converted to relative Raman intensities (Ii) using the
in various bonding, antibonding orbitals and E(2) energies have following relationship derived from the intensity theory of Raman
been calculated by natural bond orbital (NBO) analysis to give clear scattering [14,15]:
evidence of stabilization originating from the hyperconjugation of
various intramolecular interactions. The study of HOMO, LUMO f ðm0  mi Þ4 Si
Ii ¼
analysis has been used to elucidate information regarding charge mi ½1  expðhcmi =kb TÞ
transfer within the molecule. Moreover, the Mulliken population where m0 is the exciting wavenumber in cm1 (in this work, we have
analyses of the title compound have been calculated and the used the excitation wavenumber m0 = 9398.5 cm1, which corre-
calculated results have been reported. The experimental and sponds to the wavelength of 1064 nm of a Nd:YAG laser), mi the
theoretical results supported each other, and the calculations are vibrational wave number of the ith normal mode (cm1), while Si
valuable for providing a reliable insight into the vibrational spectra is the Raman scattering activity of the normal mode mi. f (is a
and molecular properties. constant equal to 1012) is a suitably chosen common normalization
factor for all peak intensities. h, k, c and T are Plank, Boltzmann
Experimental details constants, speed of light and temperature in Kelvin, respectively.
The calculated FT-Raman spectra have been plotted using pure
The compound EPDD in the solid form was purchased from Lorentizian band shape with a bandwidth of (FWHM, full width
Sigma–Aldrich Chemical Company (USA), with a stated purity of and half maximum) of 10 cm1.
greater than 98% and it was used as such without further
purification. The FTIR spectrum of molecule was recorded in the Results and discussion
region 400–4000 cm1 at a resolution of ±1 cm1 using a BRUKER
IFS-66 V FT-IR spectrometer equipped with a cooled MCT detector Geometry optimization
using KBr pellet technique. The FT-Raman spectrum of EPDD was
recorded on a BRUKER IFS-66V model interferometer equipped The geometrical structure along with numbering of atoms of
with FRA-106 FT-Raman accessory in the region 100-3500 cm1 EPDD is obtained from Gaussian 03W and GAUSSVIEW programs
Stokes region using the 1064 nm line of a Nd:YAG laser for are shown in Fig. 1. The optimized structure parameters like bond
excitation operating at 100 mW power. Five hundred scans were lengths and bond angles calculated by HF and DFT level with 6-
accumulated at 4 cm1 resolution. The reported wavenumbers 31G(d,p) basis set is shown in Table 1. This molecule has two
are believed to be accurate within ±1 cm1. OAH bond lengths, four CAN bond lengths, two NAH bond lengths,
twelve CAH bond lengths and eleven CAC bond lengths. Most of
Computational details

As the first step, the most optimized structural parameters,

energy, and vibrational frequencies of the molecule have been
calculated by using the standard HF 6-31G(d,p) basis set. This
geometry was re-optimized at B3 [5] exchange functional
combined with the LYP [6] correlation functional resulting in the
B3LYP density functional method at 6-31G(d,p) basis set. All the
computations were performed using Gaussian 03W program [7]
and Gauss-View molecular visualization program package on the
personal computer [8]. Vibrational wave numbers and geometric
parameters were used in the vibrational frequency calculations at
the HF and DFT levels to characterize all stationary points as min-
ima. The keyword FREQ was used for wavenumber calculations.
Second, a comparison is made between the theoretically calculated Fig. 1. The optimized molecular structure of EPDD.
312 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320

Table 1 Table 1 (continued)

The optimized structure parameters of EPDD [bond length (A0) and bond angle (°)]
obtained by B3LYP/6-31G(d,p) density functional calculations. Molecule B3LYP/6-31G(d,p) HF/6-31G(d,p) Experimental
C13AC12AH23 120.3 120.3 120.0
Molecule B3LYP/6-31G(d,p) HF/6-31G(d,p) Experimental
C12AC13AC14 120.3 120.4 120.0
0
Bond length (A ) C12AC13AH24 120.2 120.2 120.0
N1AC2 1.45 1.439 1.45 C14AC13AH24 119.5 119.5 120.0
N1AC6 1.368 1.353 1.369 C13AC14AH25 119.4 118.9 120.0
N1AH17 1.01 0.995 1.012 C16AC15AH26 109.5 109.5 109.5
C2AN3 1.448 1.438 1.45 C16AC15AH27 110.2 109.4 109.5
C2AH18 1.092 1.081 1.113 C15AC16AH28 109.3 108.8 109.5
C2AH19 1.1 1.086 1.113 C15AC16AH29 111.8 111.7 109.5
N3AC4 1.37 1.354 1.369 C15AC16AH30 111.3 111.9 109.5
N3AH20 1.01 0.994 1.012 H26AC15AH27 106.4 106.6 109.5
C4AC5 1.549 1.54 1.512 H28AC16AH29 107.5 107.4 109.5
C4AO7 1.222 1.198 1.208 H28AC16AH30 108.1 108.1 109.5
C5AC6 1.558 1.547 1.509 H29AC16AH30 108.7 108.8 109.5
C5AC9 1.545 1.544 1.497
C5AC15 1.554 1.55 1.523
C6AO8 1.222 1.198 1.208
C9AC10 1.403 1.393 1.337
C9AC14 1.402 1.391 1.337 the bond lengths and bond angles deviate slightly from the exper-
C10AC11 1.395 1.384 1.337
imental data [16] for both HF and DFT levels. These differences are
C10AH21 1.086 1.075 1.1
C11AC12 1.395 1.385 1.337 probably due to the theoretical calculations belong to isolated mol-
C11AH22 1.086 1.076 1.1 ecule in gaseous phase while the experimental results belongs to
C12AC13 1.395 1.383 1.337 molecule in solid state. Comparing bond lengths and angles of
C12AH23 1.086 1.076 1.1 B3LYP with those of HF, the former is bigger than the latter and
C13AC14 1.396 1.386 1.337
the B3LYP correlates well with the experimental data. The title
C13AH24 1.086 1.076 1.1
C14AH25 1.085 1.075 1.1 molecule consists of one pyrimidine ring and one phenyl ring.
C15AC16 1.53 1.528 1.523 The pyrimidine ring appears to be a little distorted from its regular
C15AH26 1.095 1.085 1.113 hexagonal symmetry as the computed bond lengths: C5AC6 > C4-
C15AH27 1.093 1.081 1.113
AC5 > N1AC2 > C2AN3 > N3AC4 > C6AN1 for EPDD. The irregular
C16AH28 1.095 1.086 1.113
C16AH29 1.094 1.084 1.113 hexagonal symmetry of the pyrimidine ring is also evident from
C16AH30 1.091 1.081 1.113 the decrease in values of the bond angles at the substitution posi-
Bond angle (°) tion. Comparing with the pyrimidine ring, the phenyl ring is not
C2AN1AC6 122.6 123.1 118.4 distorted much from its regular hexagonal symmetry. The C4AO7
C2AN1AH17 120.4 120.3 120.8 and C4AO8 bond length indicates a considerable decrease when
N1AC2AC3 109.2 109 109.5 substituted in the place of CAH. It is observed that, CAC bond
N1AC2AH18 109 108.7 109.4
length in the optimized geometry of EPDD is calculated at B3LYP/
N1AC2AH19 110.9 111.1 109.5
C6AN1AH17 116.2 116.1 120.8 6-31G(d,p) and HF 6-31G(d,p) levels, fall in the range: 1.383–
N1AC6AC5 114.6 115.2 114.0 1.403 A0 for six member ring. It is very close agreement with
N1AC6AO8 122 121.8 123.0 experimental values [17]. The average C H bond length in the aro-
N3AC2AH18 109 108.7 109.5
matic ring calculated by B3LYP/6-31G(d,p) is 1.086 A0. It is less
N3AC2AH19 110.5 110.9 109.5
C2AN3AC4 122.7 123.2 118.4 than CAH bond length present outside the ring. The aromatic bond
C2AN3AH20 120.4 120.3 120.8 distances of the title compound are found to have higher values in
H18AC2AH19 108.2 108.3 109.5 case of B3LYP calculation with respect to those of HF method
C4AN3AH20 116 116 120.8 (1.076 A0). A similar trend has also been observed in CAN bonds.
N3AC4AC5 114.5 115.1 113.9
The two CAN bond lengths are almost equal in HF and DFT meth-
N3AC4AO7 121.5 121.5 123.0
C5AC4AO7 124 123.4 123.0 ods. Moreover, the calculated values of CAH bond lengths of
C4AC5AC6 108.9 108.6 109.5 methyl part according to B3LYP and HF methods are also in good
C4AC5AC9 109.9 109.7 109.5 agreement. From the theoretical values, we found most of the opti-
C4AC5AC15 110.6 110.8 109.5
mized bond lengths are in good agreement with experimental
C6AC5AC9 107.5 107.5 109.5
C6AC5AC15 108.4 108.6 109.5
bond lengths but bond angles are slightly longer and shorter than
C5AC6AO8 123.5 123 123.0 that of experimental values. The global minimum energy is
C9AC5AC15 111.5 111.6 109.5 obtained by HF and DFT/B3LYP level using 6-31G(d,p) basis set
C5AC9AC10 120 119.9 120.0 for the title molecule are 721.2539 a.u and 725.7051 a.u.,
C5AC9AC14 121.4 121.6 120.0
respectively.
C5AC15AC16 116.3 116.5 109.5
C5AC15AH26 107.4 107.7 109.5
C5AC15AH27 106.5 106.7 109.5
C10AC9AC14 118.5 118.4 120.0 Vibrational analysis
C9AC10AC11 120.7 120.7 120.0
C9AC10AH21 119.6 119.9 120.0 The present molecule has 84 normal modes of vibrations, all ac-
C9AC14AC13 120.7 120.7 120.0 tive in infrared and Raman spectra. Detailed description of vibra-
C9AC14AH25 119.9 120.3 120.0
C11AC10AH21 119.8 119.4 120.0
tional modes can be given by means of normal coordinate
C10AC11AC12 120.3 120.4 120.0 analysis. The specific assignment to each frequency is attempted
C10AC11AH22 119.5 119.5 120.0 through potential energy distribution (PED). For this purpose the
C12AC11AH22 120.1 120.2 120.0 full set of 113 standard internal coordinates (containing 29 redun-
C11AC12AC13 119.4 119.4 120.0
dancies) for the title molecule are defined in Supplementary Table
C11AC12AH23 120.3 120.3 120.0
S1. From these, a non-redundant set of local symmetry coordinates
were constructed by suitable linear combinations of internal
Table 2
The observed FT-IR and FT-Raman bands with their relative intensities, calculated wavenumbers and assignments of EPDD.

Mode no. Experimental wavenumber HF/6-31G(d,p) B3LYP/6-31G(d,p) Assignments (% PED)

(cm1)
FTIR FTRaman Theoretical Wavenumber IIRa IRamanb Theoretical wavenumber IIRa IRamanb
(cm1) (cm1)
Unscaled Scaled Unscaled Scaled
84 – – 3687 3315 0.407 15.45 3638 3498 0.365 19.4 mNH (100)
83 – 3506vw 3685 3313 0.391 14.78 3635 3495 0.341 19.51 mNH (100)

E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320
82 – – 3379 3038 0.126 28.01 3210 3086 0.198 33.67 mCH (99)
81 – – 3375 3034 0.167 11.48 3205 3081 0.188 2.53 mCH (98)
80 – – 3365 3025 0.242 16.78 3199 3076 0.209 15.07 mCH (99)
79 – – 3352 3014 0.177 20.19 3188 3065 0.175 21.4 mCH (99)
78 3332vw – 3341 3004 0.013 13.33 3180 3057 0.025 13.26 mCH (99)
77 – – 3309 2975 0.211 7.02 3157 3035 0.193 8.08 mmCH3ip (89), mCH3op (7)
76 3217vs 3236vw 3282 2951 0.123 15.44 3121 3001 0.267 14.83 mCH3op (91), mCH3ip (6)
75 3105w – 3275 2945 0.304 22.65 3116 2996 0.253 17.87 mmCH3ss (96)
74 2993vw 3062s 3253 2925 0.368 16.48 3109 2989 0.281 24.05 mCH2ss (47), mCH2as (47)
73 2977m 3003m 3221 2896 0.188 23.75 3068 2950 0.206 22.43 mCH2ss (49), mCH2as (49)
72 2944m 2944s 3197 2874 0.341 22.34 3055 2937 0.306 24.02 mCO (74), mCN (9), btrig1 (7)
71 2885s 2887m 3194 2872 0.328 20.64 3004 2888 0.373 21.21 mCO (73), mCN (8)
70 1970vw 1963vw 1979 1779 1.000 10.42 1807 1737 1.000 11.48 xHCN (17), bCH2wa (16), bCH2ro (12), bCH2ro (11), bCH3ip (9), bCH3op (6)
69 1951vw 1942vw 1950 1753 0.981 11.31 1778 1709 0.905 10.98 mCC (67), bHCC (22), bsym2 (10)
68 1803vw – 1807 1625 0.122 21.09 1657 1593 0.139 23.5 mCC (61), bHCC (18), basym2 (8)
67 1711m 1700m 1778 1599 0.085 11.86 1635 1572 0.098 11.7 bCH3ip (65), bCH3op (11), bCH2ro (8)
66 1697m – 1676 1507 0.100 15.29 1539 1480 0.228 5.02 bHCC (62), mCC (34)
65 1668vs 1670s 1667 1499 0.205 3.87 1531 1472 0.113 13.18 bCH2sc (28), xHCN (19), bCH3ip (16), bCH3op (14), bCH2sc (6)
64 – – 1646 1480 0.703 8.17 1529 1470 0.150 18.24 bCH3op (66), bCH3ip (30)
63 – – 1645 1479 0.196 12.34 1509 1451 0.130 19.93 bCH2sc (60), bCH2ro (9), bHNC (7), bCH2wa (6)
62 – – 1628 1464 0.137 18.62 1496 1438 0.134 16.92 bHCC (47), mCC (33), bCCC (9), bCH2sc (7)
61 – – 1626 1462 0.149 6.69 1490 1432 0.191 6.1 bCH2wa (33), mCN (19), bHNC (17), bCH2tw (9), mCO (7)
60 – – 1618 1455 0.053 17.15 1487 1430 0.601 9.85 bCH2sc (22), bCH2wa (22), mCN (13), bCH3ip (12), bHNC (11), bCH3op (6)
59 1595vw 1598s 1608 1446 0.202 6.04 1478 1421 0.377 8.15 bCH3sb (41), bCH2wa (31), bCH2sc (15), mCC (6)
58 1579vw 1580m 1552 1395 0.131 5.31 1423 1368 0.171 8.14 bCH2ro (25), bCH2sc (23), bCH3ip (16), bHNC (6), bCH3op (5)
57 – – 1545 1389 0.207 8.6 1391 1337 0.244 12.33 bHNC (21), bCH2ro (18), bCH2sc (10), mCN (9), bHCC (8), bCH3ip (7)
56 1493vs – 1505 1353 0.671 9.77 1376 1323 0.261 6.34 bCH2wa (20), bHCC (13), bHNC (13), mCN (12), bCH2ro (12), mCC (10)
55 1464m 1499m 1502 1350 0.362 4.02 1374 1321 0.104 3.64 bCH2ro (26), bCH2sc (26), mCC (14), bHCC (10), bCH2tw (5)
54 1447s 1483w 1488 1338 0.220 3.58 1369 1316 0.644 12.26 bCH2wa (51), bCH2sc (24), mCC (12)
53 – 1465m 1444 1298 0.127 11.18 1342 1290 0.114 5.62 mCC (41), bCH2sc (24), bCH2ro (14), bHCC (8)
52 1401vs 1438m 1417 1274 0.044 14.28 1323 1272 0.063 11.73 bCH2ro (75), mCN (10)
51 1372vw 1410w 1377 1238 0.154 8.98 1305 1255 0.043 15.02 bCH3ip (27), bCH2wa (16), sButter (13), bCH3op (8), bCH3op (6)
50 1339m 1362w 1332 1198 0.062 9.88 1243 1195 0.132 10.66 mCN (55), mCC (13), bCH2wa (7), bONC (7), bCH2wa (5)
49 1316m – 1324 1190 0.054 13.7 1223 1176 0.073 15.07 bHCC (76), mCC (21)
48 1280s – 1310 1178 0.058 11.47 1206 1159 0.069 20.22 bCH2wa (27), mCC (17), bCH2sc (13), bCH3op (12), bCCC (6)
47 1270w 1280m 1275 1146 0.129 9.28 1190 1144 0.011 13.03 bCH (80), mCC (17)
46 – 1267w 1237 1112 0.211 13.86 1168 1123 0.132 12.04 mCC (44), bCH2wa (19), btrig2 (7), bCH (6), bCH2ro (6)
45 – – 1220 1097 0.245 11.86 1130 1086 0.203 14.82 mCC (46), mCN (20), btrig1 (6)
44 – 1206vw 1214 1092 0.149 8.81 1121 1078 0.191 7.55 mCC (45), bCH (27), bCH2wa (8), bCCC (6)
43 – – 1205 1083 0.121 12.93 1119 1076 0.251 10.29 mCN (32), mCC (24), bONC (9), bsym1 (7), bHNC (6), bCH2ro (6)
42 – 1195s 1203 1082 0.117 9.93 1113 1070 0.094 7.28 mCC (67), bHCC (17), btrig2 (7)
41 1155m 1191vw 1190 1070 0.058 1.15 1102 1059 0.192 10.07 mCN (36), mCC (28), bHNC (11), bONC (7), bCH2wa (5)
40 – 1160m 1134 1020 0.099 17.7 1060 1019 0.135 24.31 btrig2 (65), mCC (32)
39 – 1147vw 1131 1017 0.067 9.18 1018 979 0.052 17.48 xHCN (84), spuk2 (11)
38 1119vs 1112w 1116 1003 0.022 2.26 1015 976 0.146 29.98 mCC (19), bCH3ip (16), xHCN (10), sCH2 (7), bCCC (7), bCH2ro (6)
37 1076s 1105w 1097 986 0.141 10.64 1005 966 0.038 1.33 xHCN (87)
36 – 1079m 1089 979 0.092 35.74 988 950 0.017 2.74 mCC (23), bCH3op (12), bCH2ro (10), bCH2wa (10), mCN (8), btrig1 (8)
35 – – 1060 953 0.082 4.28 962 925 0.202 10.58 bCCC (25), mCC (19), bCH3ip (14), bCH2wa (10), bCH2sc (9), sbutter (5)

313
(continued on next page)
 314
Table 2 (continued)

Mode no. Experimental wavenumber HF/6-31G(d,p) B3LYP/6-31G(d,p) Assignments (% PED)

(cm1)
FTIR FTRaman Theoretical Wavenumber IIRa IRamanb Theoretical wavenumber IIRa IRamanb
(cm1) (cm1)
Unscaled Scaled Unscaled Scaled
34 – 1036s 1044 939 0.085 10.88 953 916 0.173 13.84 xHCN (55), mCC (8)
33 1036m – 1029 925 0.181 15.73 938 902 0.119 5.02 xHCN (14), bCH2ro (12), mCC (12), bCH2wa (11), xCCO (10), bCH (10)
32 1010w 1001vs 1010 908 0.224 16.76 924 888 0.162 14.8 xHCN (73)

E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320
31 997w 959m 966 869 0.026 10.74 872 838 0.021 14.94 btrig1 (43), mCN (15), basym1 (13), mCC (8)
30 954m 926m 879 790 0.253 11.02 802 771 0.201 13.88 xHCN (47), spuk2 (35), sbutter (14)
29 928w 901vw 857 771 0.106 8.52 787 757 0.114 10.78 xHCN (36), spuk2 (17), xCCO (14), mCC (10), spuk1 (8), bsym2 (6)
28 914m 841vw 835 751 0.274 6.62 766 736 0.278 9.76 spuk2 (34), xCH (24), xCCO (11), spuk1 (8), mCC (7), bsym2 (6)
27 786m 801m 805 724 0.188 3.83 733 705 0.176 9.02 xCCO (39), sast1 (15), bCCC (13), ssmt1 (8), xCH (7), sbutter (7)
26 773w – 797 717 0.175 10.53 720 692 0.249 9.47 mCC (23), bsym2 (21), xHCN (20), mCN (6)
25 763m 751vw 783 704 0.246 7.97 719 691 0.102 3.32 basym2 (81), mCC (6)
24 753w 711m 721 648 0.144 29.65 671 645 0.158 30.22 bONC (37), mCN (19), bCCC (12), sCH2 (9), xCH (8)
23 707w 670s 679 610 0.013 18.72 633 609 0.013 17.83 xHCN (39), ssmt2 (13), spuk2 (13), sbutter (7)
22 697vs 620m 651 585 0.117 11.35 598 575 0.111 11.23 xHCN (19), bONC (18), bsym2 (16), mCC (11), mCN (8)
21 655m – 604 543 0.250 12.59 557 535 0.253 13.7 xHCN (34), ssmt2 (11), bsym1 (9), mCC (9), bCH2ro (6)
20 579m 596m 590 530 0.382 21.93 549 528 0.367 21.16 bsym1 (20), sCH2 (14), bCH2sc (10), bCH2ro (9), basym1 (8), sbutter (7)
19 559m 582w 546 491 0.168 11.3 511 491 0.220 13.25 sCH2 (27), xHCN (19), basym1 (13), bCH2ro (9), sbutter (8), bCH2sc (6)
18 526s 508m 511 459 0.172 10.59 473 455 0.180 13.09 sCH2 (19), basym1 (18), sbutter (11), spuk1 (8), ssmt2 (6), sCH3 (5)
17 510vs 494vw 471 423 0.523 15.7 437 420 0.334 17.33 xHCN (50), sCH2 (16), sbutter (10)
16 464s 464m 461 414 0.197 11.83 433 416 0.480 18.78 sast2 (58), xHCN (18), ssmt2 (16), sbutter (8)
15 – – 455 409 0.114 9.49 419 403 0.037 6.55 bONC (25), mCC (21), xHCN (8), sCH2 (8), btrig1 (6), ssmt1 (5)
14 – 391s 406 365 0.160 21.3 372 358 0.146 20.49 bCCC (51), sCH2 (21), mCC (10), bONC (6)
13 – 339vw 373 335 0.189 20.16 346 333 0.198 19.36 bCCC (22), spuk1 (20), sCH2 (13), sCH3 (12), ssmt1 (5)
12 – 325m 348 313 0.118 13.14 324 311 0.128 14.13 spuk1 (27), sCH2 (26), ssmt1 (16), xHCN (16)
11 – 301m 303 272 0.037 12.19 282 271 0.045 12.25 sbutter (45), sCH2 (16), sbutter (11), sCH3 (8), bCCC (5)
10 – 258vw 279 251 0.079 16.21 255 245 0.056 15.82 sbutter (51), sCH2 (15), sCH3 (11), bCCC (5)
9 – 238vs 253 227 0.108 23.38 227 218 0.093 27.9 spuk1 (43), sCH2 (25), xHCN (15), sCH3 (7)
8 – – 219 197 0.083 7.39 203 195 0.092 7.67 sCH2 (22), sast1 (17), xHCN (16), ssmt1 (15), sbutter (10), bCCC (8)
7 – 206m 201 181 0.084 20.72 181 174 0.103 21.5 xHCN (38), sast1 (30), ssmt1 (19), sCH2 (7)
6 – 148vs 142 128 0.008 28.4 131 126 0.016 29.39 xCCC (33), ssmt1 (22), spuk1 (13), sCH3 (13), sast1 (11)
5 – 111m 126 113 0.049 22.68 116 112 0.057 20.57 sast1 (27), ssmt1 (19), sbutter (15), spuk1 (11), bCCC (6)
4 – 92vs 99 89 0.037 35.86 92 88 0.037 37.74 ssmt1 (45), spuk1 (17), sast1 (11), sCH3 (6), ssmt2 (5)
3 – – 88 79 0.052 45.59 83 80 0.060 53.78 sast1 (26), ssmt1 (25), spuk1 (21), xCCC (15), xHCN (9)
2 – – 67 60 0.098 61.33 56 54 0.110 69.69 ssmt1 (47), sast1 (40), xHCN (8)
1 – – 50 45 0.035 100 49 47 0.047 100 sbutter (36), sast1 (30), ssmt1 (23), xHCN (8)
Abbreviations: m, stretching; b, in plane bending; x, out of plane bending; s, torsion; ip, in plane; op, out of plane; ss, symmetric stretching; as, asymmetric stretching; trig, trigonal deformation; wa, wagging; ro, rocking; sc,
scissoring; tw, twisting; sym, symmetric deformation; asym, asymmetric deformation; puk, puckering; smt, symmetric torsion; ast, asymmetric torsion; butter, butterfly mode, vs, very strong; s, strong; m, medium; w, weak; vw,
very weak.
a
Relative absorption intensities normalized with highest peak absorption equal to 1.
b
Relative Raman intensities calculated by Eq. (1) and normalized to 100.
 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320 315

Fig. 2. Experimental and theoretical FTIR spectra of EPDD.

coordinates following the recommendations of Fogarasi et al. [10] coordinates that may be present in the PED distribution shown in
are summarized in Supplementary Table S2. This method is also Table 2, we have discussed here only the dominant contributions
useful for determining the mixing of other modes. But mostly the to the total potential energy of normal modes of vibration.
maximum contribution is accepted as the significant mode. The
observed FT-Raman and FT-IR bands with their relative intensities, CAH vibrations
calculated wavenumbers and assignments are given in Table 2. The Normally, CAH stretching vibrations occurs in the region 3200–
experimental FT-IR and FT-Raman spectra with corresponding the- 3000 cm1 in the heteroatomic structure and moreover these
oretically simulated FT-IR and FT-Raman spectra for EPDD are vibrations are independent in nature and position of the substitu-
shown in Figs. 2 and 3, respectively, where the calculated infrared ents [18,19]. This title molecule has two CAH moieties in pyrimi-
intensities and Raman intensities are plotted against the vibra- dine ring (ring1) and five CAH moieties in phenyl ring (ring2).
tional frequencies. In the spectra, the theoretically simulated spec- The expected seven CAH stretching vibrations are C2AH18,
tra are more regular than the experimental ones because many C2AH19, C10AH21, C11AH22, C12AH23, C13AH24 and C14AH25. For
vibrations presenting in condensed phase lead to strong perturba- 4BrMBP2CN molecule, this wavenumber is assigned at
tion of infrared and Raman intensities of many other modes. The 3025 cm1 by Sebastian et al. [20]. Sundaraganesan et al. [21] as-
RMS error of the observed and calculated frequencies (unscaled) signed CAH stretching vibrations of aromatic ring at 3066 and
of EPDD is quite obvious since the frequencies are calculated on 3075 cm1 for 2-fluoro-5-methylbenzonitrile. Accordingly, in this
the basis of quantum mechanical force fields usually differ appre- title compound, the weak intensity peak at 3332 cm1 in FT-IR is
ciably from observed frequencies. This is partly due to the neglect assigned to CH stretching vibration. No Raman peaks are observed
of anharmonicity and partly due to the approximate nature of the in the range. The calculated wavenumbers 3038, 3034, 3025, 3014
quantum mechanical methods. In order to reproduce the calcu- and 3004 cm1 in FTIR and the wavenumbers 3086, 3081, 3076,
lated frequencies, the scale factors were refined and optimized 3065 and 3057 in FT-Raman bands are assigned to CH stretching
via a least squares refinement algorithm. There are two rings pres- vibrations. As indicated by the PED, with these modes, 99% contri-
ent in EPDD molecule and hence we discuss the vibrational assign- bution comes from pure stretching vibrations. The CAH in plane
ments of these rings separately one by one. Out of several internal bending vibrations usually occurs in the region 1430–990 cm1
316 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320

Fig. 3. Experimental and theoretical FT Raman spectra of EPDD.

and is very useful for characterization purposes. The in-plane CAH vibrations. As seen from Table 2, C@O out of plane bending vibra-
bending vibrations appear in the range 1000–1300 cm1 and the tions (xCCO) contribute a little percent to some frequencies in the
CAH out of plane bending vibrations occur in the frequency range region 1036–786 cm1. The observed band at 1036, 928, 914 and
750–1000 cm1 [22,23]. For our title molecule, the CAH in-plane 786 cm1 in FTIR and 901, 841 and 801 cm1 in FT-Raman spec-
bending vibrations are observed in the region 1270–1036 cm1 trum (mode nos. 33, 29–27) are assigned to the C@O out of plane
in FT-IR and 1281–1036 cm1 in FT-Raman. The frequencies are bending mode.
calculated by HF method in the range of 1146–925 cm1 and DFT
method in the range 1144–902 cm1 (mode nos. 47–33) are well
Methylene group vibrations
correlated with the experimental frequencies. The maximum PED
The CAH stretching of the methylene groups are at lower fre-
contribution is 82% for CAH in-plane bending vibrations. The
quencies than those of the aromatic CAH ring stretching. The
CAH out of plane bending vibrations are predicted in the region
CH2 antisymmetric stretching vibrations are generally observed
983–760 cm1 are coincided very well with the observed frequen-
in the region 3000–2900 cm1, while the CH2 symmetric stretch
cies of FT-IR (914, 786, 753 cm1) and FT-Raman (841, 801,
were appearing between 2900 and 2800 cm1 [25,26]. The CH2
711 cm1). In general the aromatic CAH vibrations (stretching,
antisymmetric and symmetric stretching vibrations were observed
in-plane and out-of-plane bending) are calculated theoretically in
at 2993 and 2977 cm1 (FTIR), 3003 and 2944 cm1 (FT-Raman),
good agreement with experimentally accepted values [22,23].
respectively for EPDD molecule. The calculated antisymmetric
and symmetric CH2 stretching vibrations of the methylene group
CAO vibrations are at 2925 and 2896 cm1 (mode nos. 74 and 73) by HF method
The characteristic absorption bands of C@O stretching vibra- and 2989 and 2950 cm1 by B3LYP method. In the present assign-
tions of the title compound is very complex and appear as very ment, the order of frequency are CH2 deformation > CH2 scis > CH2
broad and strong IR bands [24]. The observed bands at 2944, wagg > CH2 twist > CH2 rock. The recorded spectrum shows only
2885 cm1 (FTIR) and 2944, 2887 cm1 (FT-Raman) cm1 can be two medium strong peaks at 1464, 1447 cm1 (FTIR) and at
assigned to the C4@O7 and C6@O8 stretching modes, respectively. 1499, 1483 cm1 (FT-Raman) are assigned to CH2 scissoring and
They were calculated by HF and B3LYP at 2874, 2872 cm1 and wagging vibrations. The computed values of both models show
3055, 3004 cm1, respectively. Although the C@O bonds in the good agreement with the above experimental data. From the
molecule have no hydrogen bonding in the solid phase, this theoretical calculations, the CH2 wagging modes are predicted at
differences between experimental and theoretical frequencies for 1353and 1338 cm1 (mode nos. 56 and 54) by HF method and at
the C@O stretching bands are due to large anharmonicity in the 1323 and 1316 cm1 by B3LYP method. It shows excellent
 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320 317

correlation with the FTIR band at 1493 and 1447 cm1 and FT-Ra- vibrations, respectively. The ring bending modes of EPDD are also
man band at 1483 cm1 and also shows the maximum PED contri- listed in Table 2. In general, the other ring stretching modes are
bution of 87%. The peaks observe at 1464 cm1 in FTIR and at in conformity with the literature values [38,39].
1499 cm1 in FT-Raman and the calculated wavenumbers
1350 cm1 in HF and 1321 cm1 in B3LYP are assigned to CH2 Molecular electrostatic potential
twisting vibrations. The CH2 rocking vibrations are also predicted
at lower wavenumbers with good correlation of experimental data. Molecular electrostatic potential (MEP) at a point in the space
around a molecule gives an indication of the net electrostatic effect
Methyl group vibration produced at that point by the total charge distribution of the mole-
Methyl groups are generally referred as electron donating sub- cule and correlates with dipole moments, electronegativity, partial
stituents in the aromatic ring system. Whenever a methyl group is charges, and chemical reactivity of the molecule. In the majority of
present in a compound, it gives rise to two asymmetric and one MEPs, while the maximum negative region which preferred site
symmetric stretching vibration [27]. The asymmetric stretch is for electrophilic attack indications as red color, the maximum posi-
usually at higher wavenumber than the symmetric stretch. The tive region which preferred site for nucleophilic attack symptoms as
asymmetric stretching vibrations of CH3 are expected in the region blue color. The color grading of resulting surface simultaneously dis-
2925–3000 cm1 and the symmetric CH3 stretching vibrations in plays molecular size, shape and electrostatic potential value which
the range 2905–2940 cm1 [28,29]. The predicted asymmetric are very useful in research of molecular structure with its physico-
and symmetric stretching vibrations for CH3 are at 3105, chemical property relationship [40,41]. The molecular electrostatic
2993 cm1 (mode no. 75 and 74) in FT-IR band and at 3062 cm1 potential (MEP) map and the electrostatic potential contour map
in FT-Raman band. FTIR band at 3217 cm1 and FT-Raman band for positive and negative potential of the title compound EPDD are
at 3236 cm1 (mode no. 76) were assigned as in-plane and out- shown in Supplementary Figs. S1 and S2. The MEP is a plot of electro-
of-plane CH3 stretching. The CACH3 vibrations usually combine static potential mapped onto the constant electron density surface.
with CAH in-plane bending vibration [19,21]. The active funda- Different values of the electrostatic potential are represented by
mental mode is observed at 1206 cm1 in FT-Raman is identified different colors. Red represents the regions of the most negative
as CACH3 stretching vibration. The CACH3 stretching mode shows electrostatic potential; blue represents the regions of the most
good agreement with computed wavenumber at 1092 cm1 in HF positive electrostatic potential. Potential increases in the order
and 1078 cm1 in B3LYP. The rocking mode of the CH3 group usu- red < orange < yellow < green < blue. The color code of this map is
ally appears in the region 1070–1010 cm1 [30–32]. Aromatic in the range between 0.09394 a.u (deepest red) and 0.09394 a.u
compounds display a methyl rocking (rCH3) in the neighborhood (deepest blue) in compound, where blue indicates the strongest
of 1045 cm1 [29]. In the present work, the rCH3 vibration is ob- attraction and red indicates the strongest repulsion. Such mapped
served at 1119 cm1 in FTIR spectrum. The theoretically calculated electrostatic potential surfaces have been plotted in B3LYP/6-
value (1070 cm1) shows good agreement with recorded spectral 31G(d,p) basis set using the computer software Gauss view. As can
data with PED contribution of 93%. The CH3 symmetry bending be seen from MEP map of the title molecule, while regions having
vibration is assigned at 1595 cm1 in FT-IR (1598 cm1 in FT-Ra- the negative potential are over the electronegative atoms (oxygen
man) was calculated at 1478 cm1 in B3LYP. The CH3 torsional atoms), the regions having the positive potential are over the hydro-
mode is expected below 100 cm1. The observed wavenumber gen atoms. The negative potential value is 0.00825473 a.u. for oxy-
(in FTRaman) at 92 cm1 (mode no. 4) is assigned to CH3 torsional gen atom. A maximum positive region localized on the hydrogen
mode, shows good agreement with computed wavenumber at atoms bond has value of +0.0932852 a.u. From these results, we
89 cm1 by HF method and 88 cm1 by B3LYP method. The methyl can say that the O atoms indicate strongest repulsion and H atoms
group assignments proposed in this study is also in agreement indicate the strongest attraction.
with the literature values [33,34].

NBO analysis
Ring vibration
The title compound consists of one pyrimidine ring and one
NBO analysis provides the most accurate possible ‘natural Lewis
phenyl ring. Most of the ring vibrational modes are affected by
structure’ picture of /, because all orbital details are mathemati-
the substitutions in the ring of the title molecule. The characteristic
cally chosen to include the highest possible percentage of the elec-
ring stretching vibrations are assigned in the region 1650–
tron density. A useful aspect of the NBO method is that it gives
1300 cm1 [35,36]. The main contributions corresponded to mode
information about interactions in both filled and virtual orbital
nos. 46, 45, 42 and 40 (trigonal bending), to nos. 31, 29, 28, 26, 25,
spaces that could enhance the analysis of intra- and intermolecular
22 and 21 (symmetry bending) and to 31, 25, 20, 19 and 18 (asym-
interactions. The second-order Fock matrix was carried out to eval-
metry bending). The presence of conjugate substituents such as
uate the donor–acceptor interactions in the NBO analysis [42]. The
CAO, CAC, CAN or the presence of heavy element causes a doublet
interactions result is a loss of occupancy from the localized NBO of
formation. Therefore, the CAC stretching vibrations of EPDD are
the idealized Lewis structure into an empty non-Lewis orbital. For
found at 1951 cm1 in FTIR and 1942 cm1 in Raman spectrum.
each donor (i) and acceptor (j), the stabilization energy E(2) associ-
The theoretically computed values for CAC vibrational modes by
ated with the delocalization i ? j is estimated as
B3LYP/6-31G(d,p) method gives excellent agreement with experi-
mental data. The identification of CAN stretching frequencies is a Fði; jÞ2
rather difficult task, since the mixing of vibrations is possible in E2 ¼ DEij ¼ qi
zj  zi
this region. The CAN stretching vibration is usually lies in the re-
gion 1400–1200 cm1. The CAN stretching is observed strongly where qi is the donor orbital occupancy, ei and ej are diagonal
at 1280 cm1 and is mixed with CAH in-plane bending vibration elements and F(i, j) is the off diagonal NBO Fock matrix element.
[37]. This frequency is also at the lower end of the expected range Natural bond orbital analysis provides an efficient method for
which may be also due to the interaction of CAC vibration, whose studying intra and intermolecular bonding and interaction among
frequency extends up to this value. In this study, the bands ob- bonds, provides a convenient basis for investigating charge transfer
served between 1493–997 cm1 and 1499–959 cm1 in FTIR and or conjugative interaction in molecular systems. Some electron
FT-Raman spectra of EPDD have been designated to CAN stretching donor orbital, acceptor orbital and the interacting stabilization
318 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320

energy resulted from the second-order micro-disturbance theory with other atoms. The maximum charge is due to the attachment
are reported [43,44]. The larger the E(2) value, the more intensive of negatively charged oxygen atoms O7 and O8.
is the interaction between electron donors and electron acceptors,
i.e. the more donating tendency from electron donors to electron HOMO–LUMO energy
acceptors and the greater the extent of conjugation of the whole
system. Delocalization of electron density between occupied Le- Many organic molecules that containing conjugated p electrons
wis-type (bond or lone pair) NBO orbitals and formally unoccupied are characterized and analyzed by means of vibrational spectros-
(antibond or Rydgberg) non-Lewis NBO orbitals are corresponded copy [47,48]. In most cases, even in the absence of inversion sym-
to a stabilizing donor–acceptor interaction. NBO analysis has been metry, the strongest bands in the Raman spectrum is weak in the
performed on the EPDD molecule using NBO 3.1 program as imple- IR spectrum and vice versa. But the intramolecular charge transfer
mented in the Gaussian 03W package at the DFT/B3LYP/6-31G(d,p) from the donor to accepter group through a single–double bond
level of theory in order to elucidate the intramolecular, rehybrid- conjugated path can induce large variations of both the molecular
ization and delocalization of electron density within the molecule. dipole moment and the molecular polarizability, making IR and
The corresponding results have been tabulated in Supplementary Raman activity strong at the same time. The experimental spectro-
Table S3. scopic behavior described above is well accounted for by ab initio
The intramolecular hyperconjugative interactions are formed calculations in p conjugated systems that predict exceptionally
by the orbital overlap between bonding CAC, CAH and antibond- large Raman and infrared intensities for the same normal modes
ing orbital which results in intramolecular charge transfer (ICT) [49]. It is also observed in out title molecule the bands in FT-IR
causing stabilization of the system. These interactions are ob- spectrum have their counterparts in Raman shows that the relative
served as increase in electron density (ED) in CAC and CAH anti- intensities in IR and Raman spectra are comparable resulting from
bonding orbital that weakens the respective bonds. The strong the electron cloud movement through p conjugated frame work
intramolecular hyperconjugative interactions of the r and p elec- from electron donor to electron acceptor groups. Highest occupied
trons of CAC, CAH bonds to the anti CAC, CAH bonds of the ring molecular orbital (HOMO) and lowest unoccupied molecular
lead to stabilization of some part of the rings as evident from orbital (LUMO) are very important parameters for quantum chem-
Supplementary Table S3. There occurs a strong intramolecular istry. We can determine the way the molecule interacts with other
hyperconjugative interaction of p electrons from C9AC10 to p(- species; hence, they are called the frontier orbitals. The orbital
C11AC12) (ED ffi 0.332e and E(2) = 22.57 kJ mol1), from C11AC12 determine the way in which the molecule interacts with other spe-
to p(C13AC14) (ED ffi 0.318e and E(2)= 21.38 kJ mol1) and from cies. HOMO, which can be thought the outermost orbital contain-
C13AC14 to p(C9AC10) (ED ffi 0.365e and E(2) = 23.06 kJ mol1). ing electrons, tends to give these electrons such as an electron
These interactions give rise to increasing the ED on p bonds lead- donor. On the other hand; LUMO can be thought the innermost
ing to stabilization of EPDD phenyl ring system with different sta- orbital containing free places to accept electrons [50]. Therefore,
bilization energies. The most important energy, related to the while the energy of the HOMO is directly related to the ionization
molecule is electron donating from LP(2) O7 to the antibonding potential, LUMO energy is directly related to the electron affinity.
acceptor r (N3AC4) and r(C4AC5) with stabilization energy Energy difference between HOMO and LUMO orbital is called as
26.53 and 22.13 kJ mol1. Further LP(2) O8 conjugate with energy gap that is an important stability for structures [51].
N1AC6 and C5AC6 through antibond i.e. r(N1AC6) and r(C5AC6) HOMO–LUMO helps to characterize the chemical reactivity and ki-
leads to stabilization energy of 26.51 and 22.14 kJ mol1, respec- netic stability of the molecule [52]. A molecule with a small gap is
tively. LP(1) N1 and LP(1) N3 give rise to stabilization of pyrimi- more polarized and is known as soft molecule. Recently, the energy
dine ring via conjugating with p(C6AO8) and p(C4AO7) leading gap between HOMO and LUMO has been used to prove the bioac-
the stabilization energy of 17.48 and 21.15 kJ mol1, respectively. tivity from intramolecular charge transfer (ICT) [53,54]. The fron-
According to Supplementary Table S3, intramolecular CAN  O tier orbitals (HOMO, LUMO) of EPDD, with its energy for B3LYP/
bond like weak interactions are exposed in the NBO analysis by 6-31G(d,p) method are plotted in Supplementary Fig. S4. The
the interaction between the O lone pair and CAN antibonding HOMO and LUMO energy gap of EPDD calculated by HF/6-
orbital (LP(1) O7 ? r N3AC4, LP(1) O8 ? rN1AC6). Notwith- 31G(d,p) and B3LYP/6-31G(d,p) methods are given in Table 3.
standing the fact that the energetic contribution (1.88 kJ mol1) According to B3LYP/6-31G(d,p) calculation, the energy band gap
of hyperconjugative interaction is weak, these E(2) values are (DE) (translation from HOMO to LUMO) of the molecule is about
chemically significant and can be used as a measure of intramo- 6.2984 eV. The highest occupied molecular orbitals are localized
lecular delocalization. mainly on both the rings.

Global and local reactivity descriptors

Mulliken atomic charges
The energy gap between HOMO and LUMO is a critical parame-
Mulliken atomic charge calculation [45,46] has a significant role ter to determine molecular electrical transport properties. By using
in the application of quantum chemical calculation to molecular HOMO and LUMO energy values for a molecule, the global
system because of atomic charges effect electronic structure,
dipole moment, molecular polarizability and other properties of Table 3
molecular systems. The calculated Mulliken charge values of EPDD HOMO–LUMO energy values of EPDD calculated by HF/6-31G(d,p) and B3LYP/6-
31G(d,p) methods.
by DFT/B3LYP and HF method using 6-31G(d,p) basis set in gas
phase are listed in Supplementary Table S4. The charge distribution Parameters (eV) Basis set/method
structure of EPDD is shown in Supplementary Fig. S3. The charge HF/6-31G(d,p) B3LYP/6-31G(d,p)
distribution of EPDD shows that the carbon atom attached with EHOMO 9.1268 6.6619
oxygen atom is positive, whereas the remaining carbon atoms ELUMO 3.5315 0.3635
are negatively charged. The nitrogen atoms N1 and N3 have more EHOMO–LUMO gap 12.6583 6.2984
negative charges whereas all the hydrogen atoms have a positive EHOMO1 9.2683 6.7817
ELUMO+1 3.6679 0.1992
charge. The maximum atomic charge is obtained for C4 and C6.
EHOMO1  ELUMO+1 gap 12.9361 6.5825
The minimum atomic charge is obtained for C9 when compared
 E. Isac Paulraj, S. Muthu / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 106 (2013) 310–320 319

chemical reactivity descriptors of molecules such as hardness, Table 4

chemical potential, softness, electronegativity and electrophilicity Chemical potential, hardness and electrophilicity index by HF/6-31G(d,p) and B3LYP/
6-31G(d,p) methods for EPDD.
index as well as local reactivity have been defined [55–59]. Pauling
introduced the concept of electronegativity as the power of an Parameters HF/6-31G(d,p) B3LYP/6-31G(d,p)
atom in a molecule to attract electrons to it. Hardness (g), chemical l = v 2.7977 3.5127
potential (l) and electronegativity (v) and softness are defined g 6.3292 3.1492
follows. S 0.1580 0.3175
x 0.6183 1.9590
   
1 @2E 1 @l
g¼ VðrÞ ¼ VðrÞ
2 @N2 2 @N
toxicity of various pollutants in terms of their reactivity and site

@E selectivity [62–64]. The calculated value of electrophilicity index
l¼ VðrÞ describes the biological activity of EPDD.
@N
 
@E Conclusion
v ¼ l ¼  VðrÞ
@N
In this study, the spectroscopic properties of the compound
where E and V(r) are electronic energy and external potential of an were examined by FT-IR and FT-Raman techniques. The FT-IR
N-electron system respectively. Softness is a property of molecule and FT-Raman spectral measurements have been made for the
that measures the extent of chemical reactivity. It is the reciprocal EPDD. Various quantum chemical calculations help us to identify
of hardness. the structural and symmetry properties of the molecule. The com-
plete vibrational assignments of wavenumbers are made on the ba-
1 sis of potential energy distribution (PED). The comparative result of
S¼
g experimental and theoretical study gave us a full description of the
Using Koopman’s theorem for closed-shell molecules, g, l and v geometry and vibrational properties of title molecule. The com-
can be defined as plete vibrational analysis, NBO analysis and HOMO–LUMO analysis
of the title compound was performed on the basis of HF and DFT/
ðI  AÞ B3LYP calculations at the 6-31G(d,p) basis set. Charge transfer oc-
g¼
2 curs in the molecule between HOMO and LUMO energies, and fron-
tier energy gap are calculated and presented. The difference
ðI þ AÞ between the observed and the scaled wave number values of most
l¼
2 of the fundamentals are very small. NBO analysis provides an effi-
cient method for studying inter and intramolecular interactions in
ðI þ AÞ molecular system. The Mulliken charges and natural atomic
v¼ charges of the title molecule have been studied by both the HF
2
and DFT methods. The consistency between the calculated and
where A and I are the ionization potential and electron affinity of experimental FT-IR and FT-Raman data indicates that the B3LYP/
the molecules respectively. The ionization energy and electron 6-31G(d,p) method can generates reliable geometry and related
affinity can be expressed through HOMO and LUMO orbital energies properties of the title compound. The MEP map shows the negative
as I = EHOMO and A = ELUMO. Electron affinity refers to the capabil- potential sites are on oxygen and nitrogen atoms as well as the po-
ity of a ligand to accept precisely one electron from a donor. How- sitive potential sites are around the hydrogen atoms.
ever in many kinds of bonding viz covalent hydrogen bonding,
partial charge transfer takes places.
Appendix A. Supplementary material
The ionization potential of the benzophenone is 9.45 eV [60].
The ionization potential calculated by HF/6-31G(d,p) and B3LYP/
Supplementary data associated with this article can be found, in
6-31G(d,p) methods for EPDD is 6.3291 eV and 3.1492 eV respec-
the online version, at http://dx.doi.org/10.1016/j.saa.2013.01.048.
tively. It has lower potential than that of benzophenone. Consider-
ing the chemical hardness, large HOMOLUMO gap means a hard
References
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