Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 157167

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

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

Vibrational spectra of 3,5-diamino-6-chloro-N-(diaminomethylene) pyrazine-2-carboxamide: Combined experimental and theoretical studies

S. Sakthivel a, T. Alagesan b, Abdulaziz A. Al-Saadi c, S. Renuga d, S. Muthu e,
a

Department of Physics, Panimalar Engineering College, Chennai, Tamil Nadu, India Department of Physics, Presidency College, Chennai, India Department of Chemistry, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia d Department of Physics, Indira Institute of Engineering and Technology, Thiruvallur, Tamil Nadu, India e Department of Physics, Sri Venkateswara College of Engineering, Sriperumbudur, India
b c

h i g h l i g h t s
 FTIR, FT-Raman and UVVis

g r a p h i c a l a b s t r a c t
A complete vibrational analysis of 3,5-diamino-6-chloro-N-(diaminomethylene)pyrazine-2-carboxamide is performed by combining the experimental and theoretical information using Pulays density functional theory (DFT) based on scaled quantum chemical approach. The calculated HOMO and LUMO energies show that charge transfer occurs 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.

investigations of 3DCNDPC were carried out.  Molecular structure was studied using B3LYP/6-311++G(d,p) method.  The PED calculation provides a strong support for the frequency assignment.  NBO analysis used to explain the interaction between electron donors and acceptors.

a r t i c l e

i n f o

a b s t r a c t
In this work, the vibrational spectral analysis of 3,5-diamino-6-chloro-N-(diaminomethylene)pyrazine2-carboxamide(3DCNDPC) was carried out using FT-Raman and FT-IR spectroscopy in the range 400050 cm1 and 4000500 cm1 respectively. The experimental spectra were recorded in the solid phase. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT) B3LYP with the standard basis set 6-311++G(d,p). The optimized geometric parameters (bond lengths and bond angles) were compared with experimental values. Normal co-ordinate calculations were performed with the DFT force eld corrected by a recommended set of scaling factors yielding fairly good agreement between observed and calculated frequencies. Simulation of infrared and Raman spectra utilizing the results of these calculations led to excellent overall agreement with the observed spectral patterns. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated with scaled quantum mechanics

Article history: Received 30 November 2013 Received in revised form 25 January 2014 Accepted 11 February 2014 Available online 26 February 2014 Keywords: FTIR FT-Raman DFT NBO PED

Corresponding author. Tel.: +91 9443690138; fax: +91 4427162462.

E-mail addresses: muthu@svce.ac.in, mutgee@gmail.com (S. Muthu). http://dx.doi.org/10.1016/j.saa.2014.02.066 1386-1425/ 2014 Elsevier B.V. All rights reserved.

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(SQM) method. The stability of the molecule arising from hyper conjugative interactions and the charge delocalization has been analyzed by using Natural Bond Orbital (NBO) analysis. UVVis spectrum of the compound was recorded. The calculated HOMO and LUMO energies show that chemical activity of the molecule. 2014 Elsevier B.V. All rights reserved.

Introduction 3DCNDPC is a biologically active drug which is used to treat congestive heart failure, hypertension. It was also tested as treatment of cystic brosis [1]. It is a guanidinium group containing pyrazine derivative. 3DCNDPC works by directly blocking the epithelial sodium channel (ENaC) thereby inhibiting sodium re-absorption in the late distal convoluted tubules, connecting tubules, and collecting ducts in the kidneys [2]. It is white crystalline powder, slightly soluble in water. Biophysical and molecular properties of 3DCNDPC has been analyzed by Matalon et al. [3]. The characteristics and regulatory mechanisms of title molecule on sensitive in nonepithelial cells, such as vascular smooth muscle, oocytes, human and rat lymphocytes respectively [4,5]. The derivatives of title compound and their kaliuretic effects has been carried out in recent years [6,7]. There are some limitations on the use of the title compound in early handling of renal failures [8,9]. Simultaneous determination of the title molecule reversed phase liquid chromatography and the optimized method proved to be specic, robust and accurate for its quality control in pharmaceutical preparations had reported earlier [10]. Due to the above biological importance of our compound, in our interest to report a conclusive conformational and vibrational study with the help of DFT/B3LYP/6-311+G(d,p) calculations as well as infrared, Raman and UVVis spectroscopic techniques. Density functional theory [11] has been reported to provide excellent vibrational frequencies of organic compounds if the calculated frequencies are scaled to compensate for the approximate treatment of electron correlation, for the anharmonicity effect [12 14]. In this work, detailed vibrational and electronic structure theory studies of 3DCNDPC were performed using the scaled quantum mechanical (SQM) force eld technique based on DFT calculations [15]. The method predicts relatively accurate molecular structure and vibrational spectra with moderate computational effort. The redistribution of electron density (ED) in various bonding and antibonding orbitals and E(2) energies have been calculated by Natural Bond Orbital (NBO) analysis using DFT method to give clear evidence of stabilization originating from the hyperconjugation of various intramolecular interactions. The HOMO and LUMO analyses have been used to elucidate information regarding charge transfer within the molecule. In addition, MEP, Mulliken population analysis, hyperpolarizability and thermodynamic properties are also calculated. Experimental details

correction according to the fourth power scattering factor was performed, but no instrumental correction was done. The ultraviolet absorption spectrum of sample solved in water was examined in the range 200800 nm by using Cary 5E UVVis NIR recording spectrometer. The spectral measurements are carried out at Sophisticated Analytical Instruments Facility (SAIF), Indian Institute of Technology (IIT), Chennai. Computational details The optimized molecular structure, molecular electrostatic potential and vibrational spectra of the title compound were calculated using DFT with Becke3LeeYangParr (B3LYP) combined with 6-311++G(d,p) basis set using Gaussian 03 program package [16] and Gauss-view molecular visualization program package on a personal computer [17]. Scaling of the force eld was performed according to the SQM procedure [18,19] using selective scaling in the normal internal coordinate representation [20]. The scale factor calculation and characterization of the normal modes using potential energy distribution (PED) were done with the MOLVIB 7.0 program written by Sundius [21]. The Raman activities (Si) calculated by Gaussian 03 program have been suitably adjusted by the scaling procedure with MOLVIB and subsequently converted to relative Raman intensities (Ii) using the following relationship derived from the basic theory of Raman scattering [22,23].

Ii

f t0 t1 4 Si ti 1 exphcti =kb T

where t0 is the exciting frequency (in cm1), ti is the vibrational wave number of the ith normal mode, h, c and kb are universal constants, and f is the suitably chosen common scaling factor for all the peak intensities. For the plots of simulated IR and Raman spectra, pure Lorentzian band shapes are used with full width at half maximum of 10 cm1. The Natural Bonding Orbital (NBO) calculation was performed using NBO 3.1 program [24] and was carried out in the Gaussian 03W package at the DFT/B3LYP level. The hyperconjugative interaction energy was deducted from the second order perturbation approach [2527]. UVVis spectra, electronic transition, vertical excitation energies, absorbance and oscillator strengths were computed with the time-dependent DFT method. Results and discussion Rotational conformers and molecular geometry

High grade pure sample 3DCNDPC was purchased from Sigma Aldrich chemical company with a stated purity 97% and it was used without further purication. The FT-IR spectrum was recorded in the region 4000500 cm1, with sample in the KBr pellet, using Nicolet Magna 560 FTIR spectrometer. The resolution of the spectrum is 4 cm1. The FT-Raman spectrum was obtained in the range 400050 cm1 using Bruker RFS 100/S FT Raman spectrophotometer with a 1064 nm Nd:YAG laser source of 100 mW power. Liquid nitrogen cooled Ge-diode was used as a detector. Spectra were collected for samples with 1000 scan accumulated for over 30 min duration. The spectral resolution after apodization was 2 cm1. A

To found stable conformers, a meticulous conformational analysis was carried out for the title compound. Rotating 10 each degree intervals around the free rotation bonds, conformational space of the title compound was scanned by semi empirical Merck Molecular Force Field (MMFF) method [28] and then full geometry optimizations of these structures were performed by B3LYP/6311++G(d,p) level. Results of geometry optimizations indicated that the title compound has nine conformers as shown in Fig. 1. Total energies and relative energies of conformers were calculated by DFT/B3LYP with 6-311++G(d,p) level, are presented in Table 1.

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159

The calculations performed reveals that the conformer C1 acquires the dominant stability among others. This form is believed to be mainly stabilized by the prevailed conjugation effect throughout the molecules skeleton. The pronounced conjugation in 3DCNDPC can be clearly noticed with the sp2 hybridization retained by the three NH2 groups (the two substituents on the pyrazine ring and the one boned to the C18 atom). The intramolecular hydrogen bonding also plays a signicant role to maintain the very closely planar structure for the most stable conformer. The optimized structural parameters (bond length and bond angle) were also calculated by DFT/B3LYP with 6-311++G(d,p) basis set, which are presented in Table 2. The atom numbering scheme adopted in this study is given in Fig. 2. The optimized structure of the title compound was compared with other similar system for which the crystal structure has been solved. From theoretical values we can nd the most of the optimized bond lengths and bond angles are slightly larger and smaller than experimental values [29]. Comparing bond angles and bond lengths of 3DCNDPC at B3LYP/6-311++G(d,p) level leads to geometrical parameters which are much closer to experimental values. This is due to the theoretical calculations are performed for an isolated molecule in gaseous phase and the experimental results are for a molecule in a solid state. This molecule has three CAC bond lengths, one CAO bond length, six NAH bond lengths, eight CAN bond lengths and one CACl bond length. It is observed that the calculated CAC bond distances are higher than the CAN bond lengths, they are found to be slight difference at all levels of calculations. The NAC bond distances calculated by DFT method are higher than the experimental result but NAH bond length is very small compare than other bond lengths. The C@O bond length of 1.241 which is slightly larger than the experimental value and this is caused by the inter-molecular hydrogen bonding in crystalline state. The inclusion of polarization functions is important to have a better agreement with experimental geometry. From Table 2, the very largest deviation for the bond angles from the experimental values are found for C14AN16AC18,

Table 1 Total energies and relative energy for nine conformers of title compound calculated by B3LYP/6-311++G(d,p) method. Conformers C1 C2 C3 C4 C5 C6 C7 C8 C9 Total energy (Hartree) 1152.427789 1152.426065 1152.423291 1152.411931 1152.40826 1152.408913 1152.407274 1152.404266 1152.400197 Relative energy(kcal/mol) 0.000 1.082 2.823 9.951 12.255 11.845 12.874 14.761 17.314

N19AC18AN21, C18AN19AH20 bonds by 9 due to buttery mode of vibration. The calculated bond angles CACAN, CACACl, NACACl, HANAH bond angle values are in good agreement with the experimental ones. These deviations are small. For example, in this molecule the bond angle N19AC18AN21 is 129.0 while at ortho C18AN21AH22 is 117.6 and meta position angle is 111.6. This is clearly due to the high electro negativity of chlorine. The variation in bond angle depends on the electro negativity of the central atom, and the presence of lone pair of electrons and the conjugation of the double bonds. The dipole moment of title molecule is 4.3805 D. The dipole moment of a bond depends on the differences in electro negativity between the two atoms in the bond. Dipole moment increase can be attributed to hyper-conjugated structures, thereby shortening the bond lengths. It is mainly used to study the intermolecular interactions involving the van der Waal type dipoledipole forces, etc., because, larger dipole moment is stronger will be the intermolecular interactions. NBO analysis NBO analysis provides the most accurate possible natural Lewis structure picture of u, because all the orbital details are

Fig. 1. Nine possible conformers of title molecule.

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Table 2 Optimized geometrical parameters bond length, bond angle of title compound by B3LYP/6-311++G(d,p) in comparison with experimental data. Parameters Bond length() C1AC2 C1AN6 C1AN10 C2AN5 C2AC14 C3AC4 C3AN5 C3ACl13 C4AN6 C4AN7 N7AH8 N7AH9 C10AN11 C10AN12 C14@O15 C14AN16 N16AH17 N16AC18 C18AN19 C18AN21 N19AH20 N21AH22 N21AH23 Bond angle () C2AC1AN6 C2AC1AN10 N6AC1AN10 C1AC2AN5 C1AC2AC14 N5AC2AC14 C4AC3AN5 C4AC3ACl13 N5AC3ACl13 N6AC4AC3 C3AC4AN7 N6AC4AN7 C2AN5AC3 C1AN6AC4 C4AN7AH8 C4AN7AH9 H8AN7AH9 C1AN10AH11 C1AN10AH12 H11AN10AH12 C2AC14AO15 C2AC14AN16 O15AC14AN16 C14AN16AH17 C14AN16AC18 H17AN16AC18 N16AC18AN19 N16AC18AN21 N19AC18AN21 C18AN19AH20 C18AN21AH22 C18AN21AH23 H22AN21AH23
a

B3LYP/6-311++G(d,p) DFT 1.426 1.345 1.348 1.343 1.479 1.428 1.294 1.765 1.327 1.353 1.006 1.007 1.012 1.006 1.241 1.365 1.013 1.411 1.281 1.371 1.017 1.014 1.006 120.4 122.7 117.0 119.1 122.7 118.2 121.4 119.7 118.9 119.6 122.0 118.4 120.3 119.3 121.0 118.5 120.1 118.6 118.6 122.8 121.6 114.7 123.8 116.6 129.7 113.7 115.6 115.4 129.0 111.6 117.5 117.1 118.6 Expta 1.337 1.260 1.266 1.260 1.351 1.152 1.260 1.719 1.260 1.266 1.050 1.050 1.266 1.266 1.208 1.260 1.050 1.260 1.266 1.260 1.050 1.050 1.050 120.0 120.0 120.0 120.0 120.0 125.0 125.0 117.5 117.5 117.5 120.0 117.5 115.0 115.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0

Fig. 2. Atom numbering scheme adopted in the optimized structure of 3DCNDPC.

E2 DEij

qi F ij 2 ej ei

Taken from Ref. [29].

where qi is the donor orbital occupancy, ej and ei are diagonal elements and Fij is the off diagonal NBO Fock matrix element. NBO analysis provides an efcient method for studying intra and intermolecular bonding and interaction among bonds, and also provides a convenient basis for investigation charge transfer or conjugative interactions in molecular system [31]. In Table 3, the perturbation energies of signicant donoracceptor interactions are presented. The intramolecular hyper conjugative interactions are formed by the orbital overlap between r and p (CAC, CAN, C@O, CAH and NAH) bond orbitals which results ICT causing stabilization of the system. These interactions are observed as increase in electron density (ED) in CAC, CAH, CAO and NAH antibonding orbital that weakens the respective bonds. The electron density of two conjugated single as well as double bond of title compound (1.9e) clearly demonstrate strong delocalization for title molecule. The strong intramolecular hyper conjugative interaction of the r and p electrons of NAH to the anti C@O bond of the ring leads to stabilization of some part of the ring as evident from Table 3. For example the intramolecular hyper conjugative interaction of r (N16AH17) distribute to r(C18AN21), p(C14AO15), leading to stabilization of 5.42 kJ/ mol. The important interaction energy, related to the resonance in the molecule, is the electrons donating from r (LP N21) and p(LP N19) to the antibonding acceptor r(LPC18), r(LPC18), r(C18AN21), r(N19AH20) has moderate stabilization energy of 32.93, 55.68, 10.93 and 16.16 kJ/mol respectively. Furthermore, the most important interaction is the electrons donating from donator p(C4AN6), p(C3AN5) to the antibonding acceptor p(C1AC2), p(C4AN6) has strong stabilization energy of 73.81, 166.12 kJ/mol as shown in Table 3 which quantity extend the intermolecular hydrogen bonding. Vibrational analysis The vibrational spectral assignments of 3DCNDPC have been carried out with the help of PED analysis. The detailed description of vibrational modes can be given by normal coordinate analysis. The internal coordinates describe the position of the atoms in terms of distances and angles with respect to an origin atom. The symmetry coordinates are constructed using the set of internal coordinates. In this study, the full sets of 77 standard internal

mathematically chosen to include the highest possible percentage of the electron density. A useful aspect of the NBO method is that it gives information about interactions in both lled and virtual orbital spaces that could enhance the analysis of intra and intermolecular interactions. The second-order Fock matrix was carried out to evaluate the donoracceptor interactions in NBO analysis [30]. The interactions result is the loss of occupancy from the localized NBO of the idealized Lewis structure into an empty non-Lewis orbital. For each donor (i) and acceptor (j), the stabilization energy E(2) associated with the delocalization i ? j is estimated as

S. Sakthivel et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 157167 Table 3 Second order perturbation theory analysis of Fock matrix in NBO basis. Donor (i) C1AC2 C1AC2 Type ED(e) 1.98531 1.57857 Acceptor (j) C2AN5 C14AN16 C3AN5 C4AN6 C14AO15 C1AC2 C2AC14 C4AN7 C2AN5 C1AC2 C1AN10 C3ACl13 C1AC2 C1AN6 C2AC14 C3AC4 C1AC2 C4AN6 C2AN5 C4AN6 C1AN10 C3AC4 C3ACl13 C1AC2 C3AN5 C3AN5 C4AN6 C4AN6 C14AO15 C18AN21 C18 C1AC2 C2AC14 C1AC2 C3AC4 C2AC14 C14AN16 C18 C14AO15 N16AC18 C18 C18AN21 N19AH20 C18 C4AN6 C1AC2 Type ED(e) 0.02420 0.07678 0.41483 0.35360 0.16146 0.04658 0.07640 0.03067 0.02420 0.04658 0.02747 0.05397 0.04658 0.03432 0.07640 0.05463 0.32302 0.35360 0.02420 0.03445 0.02747 0.05463 0.05397 0.32302 0.41483 0.03517 0.03517 0.35360 0.16146 0.07454 0.76974 0.04658 0.07640 0.04658 0.05463 0.07640 0.07678 0.76974 0.02501 0.09845 0.76974 0.07454 0.05660 0.76974 0.03517 0.32302 E(2)a (kJ/mol) 1.49 1.70 22.18 14.51 16.80 1.42 2.47 3.27 3.03 1.94 2.66 3.95 1.46 3.00 2.42 1.54 16.50 21.42 2.26 3.16 3.28 1.86 3.63 23.21 20.19 2.79 2.79 4.19 5.42 3.41 24.21 6.92 2.19 7.61 7.58 16.86 22.84 32.38 8.79 22.87 55.68 10.93 16.16 32.93 166.12 73.81 E(j) E(i)b (a.u.) 1.18 1.06 0.24 0.26 0.25 1.35 1.15 1.13 1.16 1.35 1.15 0.93 1.22 1.12 1.17 1.35 0.32 0.29 1.15 1.16 1.14 1.33 0.92 0.31 0.25 1.16 1.07 0.61 0.61 0.98 0.38 0.92 0.72 0.91 0.89 0.64 0.60 0.21 0.82 0.58 0.16 0.61 0.77 0.20 0.02 0.03

161

F(i, j)c (a.u.) 0.038 0.039 0.065 0.056 0.062 0.039 0.048 0.054 0.053 0.046 0.049 0.054 0.038 0.052 0.048 0.041 0.066 0.072 0.046 0.054 0.055 0.045 0.052 0.075 0.065 0.051 0.049 0.049 0.053 0.052 0.108 0.072 0.036 0.075 0.074 0.094 0.105 0.088 0.079 0.104 0.092 0.080 0.110 0.088 0.087 0.073

p
r

C1AN6

1.98232

C1AN10 C2AN5

r r

1.98789 1.97522

C2AC14 C3AN5 C3AN5 C3ACl13 C4AN6

r r

1.97898 1.98561 1.71783 1.98694 1.97743

p
r r

C4AN6 C4AN7 N7AH8 N7AH9 N16AH17 N19AH20 N5 N6 O15 N16 N19 N19

p
r r r r r
LP(1) LP(1) LP(2) LP(1) LP(1) LP(2)

1.67111 1.98882 1.97930 1.97444 1.95456 1.82304 1.99932 1.99935 1.88717 1.99930 1.99916 1.58104

r r p p p r r r r r r r r r r r p p r r r r r p p r r p p r
LP(2)

r r r r r r
LP(1)

r r
LP(1)

r r
LP(1)

N21 C3AN5 C4AN6

a b c

LP(1)

p p

1.85117 0.41483 0.35360

p p

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

coordinates for title compound were dened as given in Table 4 and are summarized in Table 5 according to Pulays recommendations [32]. The experimental and calculated FT-IR and FT-Raman spectra are shown in Figs. 3 and 4, respectively. The scaled calculated harmonic vibrational frequencies at B3LYP level, observed vibrational frequencies and detailed PED assignments are tabulated in Table 6. To our knowledge, there are no theoretical studies on the vibrational assignments of 3DCNDPC in the literature. So, detailed vibrational assignments of 3DCNDPC are introduced. We have performed computational analysis done by using PED analysis and the visualization of modes. The observed slight disagreement between theoretical and experimental could be noted that the calculations were made for a free molecule in vacuum, while experiments were performed for solid samples. Furthermore, the anharmonicity is neglected in the real system for the calculated vibrations. NH vibrations It is stated that in amines, the NH stretching vibrations occur in the region 35003300 cm1. The asymmetric ANH2 stretching vibration appears from 3500 to 3420 cm1 and the symmetric

ANH2 stretching is observed in the range 34203340 cm1 [33]. With the above reference, the NAH asymmetric stretching band identied at 3560 cm1 in FT-Raman spectrum and symmetric stretching bands are identied at 3549, 3541 cm1 in both spectra with maximum contribution of PED. The two strong bands observed at 3537, 3443 cm1 in FT-IR and one weak band identied at 3414 cm1 in FT-Raman spectrum are assigned to the NH2 asymmetric stretching modes. Similarly two bands identied in FT-Raman and one band observed at FT-IR spectrum is assigned to the NH2 symmetric stretching modes with maximum contribution of PED. For amino group the NH2 scissoring identied at 1620 cm1 in FT-IR and at1599 cm1 in FT-Raman spectrum. Therefore the very weak band observed in FT-IR at 1579 cm1 is assigned to the deformation mode of the amino group. The amino rocking mode normally appears in the range 1150900 cm1 while the wagging bands between 850 and 500 cm1. Therefore, the bands at 1160, 1057, 720 and 687 cm1 are attributed to the wagging and twisting modes of amino group, respectively. The computed wave numbers identied at 1007, 763 cm1 are assigned for CANH and CANH2 wagging modes respectively. The NH2 deformation vibrations are not much affected by the hetero ring.

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Table 4 Vibrational assignment of 3DCNDPC by normal coordinate analysis based on SQM force eld calculations. S. No. Observed frequencies (cm1) FT-IR 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 3549w 3537s 3443s 3381vw 1633s 1626vw 1620vw 1579vw 1500s 1490ms 1423s 1409ms 1382s 1300s 1232s 1160vw 1139w 1089vw 1000vw 922s 779s 770ms 730wv 722w 670s 653s 619s 588s 560ms 517s FT-Raman 3560vw 3541vw 3414w 3324w 3300s 1630ms 1599s 1564w 1503s 1457s 1384s 1336ms 1266vs 1137s 1083s 1057ms 1010s 920ms 887w 789s 744s 720s 687ms 609s 581s 540vs 518w 475s 351s 282s 258vs 219s 174s 103w Calculated frequencies (cm1) DFT/6-311++G(d,p) Unscaled 3738 3704 3690 3608 3571 3531 3517 3509 1709 1698 1648 1627 1612 1586 1542 1524 1491 1453 1433 1395 1314 1255 1185 1160 1135 1110 1073 1024 936 905 791 776 750 747 738 733 706 688 660 621 600 577 530 525 486 471 428 393 374 357 351 303 295 276 228 215 155 110 98 96 78 53 44 Scaled 3561 3548 3535 3457 3421 3383 3369 3362 1637 1627 1620 1599 1585 1559 1516 1498 1465 1428 1408 1372 1292 1234 1165 1140 1116 1091 1055 1007 920 890 778 763 737 734 725 721 694 676 649 610 590 567 521 516 478 463 421 386 368 351 345 298 290 271 224 211 152 108 96 94 77 52 43 IRa 8 12 10 15 8 13 1 15 63 24 25 100 27 9 30 43 17 10 18 8 4 37 3 23 0 5 13 0 5 5 3 0 1 6 2 5 1 3 0 1 6 12 3 2 1 0 2 1 16 1 2 17 2 0 1 1 0 0 2 14 6 0 0 Ramanb 16 27 26 83 12 76 100 18 49 44 4 21 21 20 61 28 1 17 2 76 32 42 18 4 3 1 0 4 6 1 0 1 11 0 0 0 0 0 0 0 1 1 1 0 0 3 1 3 2 0 1 0 0 1 1 0 0 0 1 0 0 0 0 NHass(100) NHss(100) NH2ass(100) NH2ass(100) NH2ass(100 NH2ss(100) NH2ss(100) NH2ss(100) cC@O(94) cCN(74), cCC(25) cCN(82), NH2sci(18) cCN(68), NH2sci(30) cCC(73), dNH2 cCC(54) cCC(51) cCC(56) cCC(29), cCANH2(26) cCC(33) cCN(93) bNH(32), cCN(63) cCN(41) cCN(48), dC@O(16) NH2rok(94) Rtrigd(36), cCCl(35), cCC(19) Rsymd(58), cCC(15), cCCl(15) Rasym(60), c CCl(14), cCC(11) NH2rok(53) bCANH(35), NH2rok(42) cCC(32), NH2rok(16) c CCl(70), Rasym(13), NH2rok(10) cCC(41) xCANH2(62), xNH(16) C@Oopb(ns have e of CFA575 and 83), dONC(13) cCC(53), cCO(17), Rasmd(14) sRpuk(62), xCN(18) xNH2(82) xNH2(60) spuk(62), xCN(18), CCCipb(16) cCCN(59), bring(21), cCC(10) cCCl(56), ssmt(25) CCCipb(15), bCCC(10) CAClipb(24), xCCC(12) NH2rok(11), sring(40) xCCC(27), Rasmd(23) cCCl(58), sRasym(18), CCipb(11) C@Oopb(55), bCCl(32) sring(63), CNwag(15) CCopb(65), sCCl(24) bCANH2(60) xCN(30) sCANH2(60) sHNC(56), bring(38), cCCN(27) bCN(23), xCNC(10) sbuttery(30) + bCCN(32) bCNC(42) CClopb(60) CClopb(40), sCANH2(40) sButt(48), sRpuk(28) xNC(76) xNC(34) xNC(30), sCCN(22) sCCN(56) sCCN(36) Vibrational modes (>10% PED)

Abbreviations: s strong; vs very strong; ms medium strong; w weak; vw very weak; c stretching; b bending; s torsion; IPb In plane bending; Opb Out of plane bending; Ips In plane stretching; Ops Out of plane stretching; sci scissoring, wag wagging, twi twisting, rok rocking, trgd trigonal deformation, smd symmetric deformation, asmd asymmetric deformation, smt symmetric torsion, asmt asymmetric torsion, puk puckering, butt buttery. a Relative absorption intensities normalized with highest peak absorption equal to 100. b Relative Raman activities normalized to 100.

S. Sakthivel et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 157167 Table 5 The UVVis excitation energy DE and oscillator strength (f) for 3DCNDPC calculated by TD-DFT/6-311++G(d,p) method. States S1 S2 S3 kobs (nm) 340 280 220 kcal (nm) 240.41 213.85 200.06 Excitation energy (eV) 5.1573 5.7978 6.1973

163

Oscillator strength (f) 0.0029 0.0179 0.4000

Table 6 Mulliken atomic charges of title compound obtained by B3LYP/6-311++G(d,p) method. S. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Atom C C C C N N N H H N H H Cl C O N H C N H N H H Charge 0.06478 0.10142 0.073582 0.58887 0.20019 0.24812 0.28671 0.266877 0.280424 0.41226 0.346854 0.294726 0.433763 0.14607 0.43513 0.24866 0.400382 0.119944 0.33743 0.207366 0.43908 0.297108 0.257761

Fig. 3. FT-IR spectra of 3DCNDPC: (A) experimental and (B) B3LYP/6-311++G(d,p).

absorption band. In the present study the carbonyl-stretching vibrations are found in the region of 17801700 cm1 [36]. In our present study, the strong band at 1633 cm1 in FT-IR and 1630 cm1 as a medium band in FT-Raman spectrum are assigned to C@O stretching vibration shows small deviation calculated by B3LYP/6-311+G(d,p) method at 1637 cm1 with PED contribution of 94% (mode No. 9), the shift of the C@O stretching frequency to the low frequency side indicate the presence of a strong intermolecular hydrogen bonding, as discussed above in this manuscript. The C@O out of plane bending are observed as intense bands in the IR spectrum in the expected regions [37] at 744 and 463 cm1 respectively. The bands are separately identied by the computational results with 83% and 55% with PED contribution. CACl vibrations The vibrations belonging to the bond between the ring and the halogen atoms are worth to discuss here, since mixing of vibrations are possible due to the lowering of the molecular symmetry and the presence of heavy atoms on the periphery of molecule. Generally, the CACl absorption is obtained in the broad region between 850 and 550 cm1 [38]. Therefore, the strong band found at 887 cm1 in the FT-IR spectrum has been designated to CACl stretching mode of vibration with 70% PED contribution. The band identied at 560 cm1 in IR and at 540 cm1 in Raman is assigned to the CACl in-plane mode. These are in good agreement with the literature data [39]. Ring vibrations Many ring modes are affected by the substitutions in the ring of 3DCNDPC. The actual position of these modes determined not so much by the natural of the substituents but by the form of substitution around the ring system [40]. In our present study the wave

Fig. 4. FT-Raman spectra of 3DCNDPC: (A) experimental and (B) B3LYP/6311++G(d,p).

These amino vibrations are also in good agreement with literature values [34]. C@O vibrations The carbonyl stretching frequency has been most extensively studied by infrared spectroscopy [35]. This multiple bonded group is highly polar and therefore gives rise to an intense infrared

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number computed at 1627, 1620, 1599, 1585, 1559, 1516, 1498, 1465, 1428, 1408, 1372, 1292, 920, 778, 734, 649 cm1 by B3LYP/ 6-311++G(d,p) method (modes 1022, 29, 31, 34, 39) are assigned to CAC and CAN stretching vibration for title molecule shows good agreement with recorded spectra. The in-plane deformation vibrations are at higher wave number than the out-of-plane vibrations are presented in table Shimanouchi et al. [41] gave the wave number data for these vibrations for ve different benzene derivatives as a result of normal coordinate analysis. The in-plane and out-ofplane bending vibration are computed by B3LYP/6-311++G(d,p) method shows good agreement with literature [42,43] and recorded spectral data.

UVVis spectra analysis The UVVis spectral analysis of 3DCNDPC have been calculated by TD-B3LYP/6-311++G(d,p) method along with measured UVVis data are summarized in Table 7. Gauss-Sum 2.2 Program [44] has been used to calculate group contributions to the molecular orbitals and prepare the density of the state (DOS) as shown in Fig. 5. The DOS spectra were created by convoluting the molecular orbital information with GAUSSIAN cures of unit height. The calculated visible absorption maxima of kmax which are function of the electron availability have been reported in Table 7. The calculations of molecular orbital geometry show that the visible absorption maxima of this molecule correspond to the electron transition between frontier orbitals, such as translation from HOMO to LUMO as can be seen from the UV vis spectra absorption maxima values have been found to be 340.0, 280.0 and 220.0 nm. The kmax is a function of substitution, stronger than donor character of the substitution, the more electrons pushed into the ring, the larger kmax values may be slightly shifted by solvent effects. The role of substituents and solvent are inuence on the UV spectrum. This band may be due to electron transition of the ring to amine through bridge [transition of p] and the calculated results involving the vertical excitation energies, oscillator strength (f) and wave length. TD-DFT (B3LYP) with 6-311++G(d,p) predict one intense electronic transition at eV (200.06 nm) with an oscillator strength f = 0.4000 is good agreement with the measured experimental data (kmax = 220 nm) as shown in Fig. 6. The Highest Occupied Molecular Orbitals (HOMOs) and Lowest Unoccupied Molecular Orbitals (LUMOs) are named as Frontier molecular orbitals (FMOs). The energy gap between the HOMOs and LUMOs is the critical parameters in determining molecular electrical transport properties helps in the measure of electron conductivity. To understanding the bonding feature of the title molecule, plot of the Frontier orbitals, the Highest Occupied Molecular Orbitals HOMO and lowest Unoccupied Molecular Orbitals LUMO as shown in Fig. 7. The HOMO shows that the charge density localized mainly on carbonyl and amine group where as LUMO is localized on ring system.

Fig. 5. The calculated TDOS diagram for title compound.

Fig. 6. UVVis spectra of title compound.

Molecular electrostatic potential maps MEP is related to the electronic density and is a very useful descriptor in understanding sites for electrophilic and nucleophilic reactions as well as hydrogen bonding interactions [45,46]. The electrostatic potential V(r) is also well suited for analyzing processes based on the recognition of one molecule by another, as in drug-receptor, and enzyme substrate interactions, because it is through their potentials that the two species rst see each other [47]. To predict reactive sites of electrophilic and nucleophilic attacks for the investigated molecule, MEP at the B3LYP/6311++G(d,p) optimized geometry was calculated. The different values of the electrostatic potential at the surface are represented by different colors. Potential increases in the order red1 < green < blue < pink < white. The color code of these maps is in the range between 0.0500 a.u. (red) to 0.0500 a.u. (white) in compound, where blue indicates the strongest attraction and red indicates the strongest repulsion. Regions of negative V(r) are usually associated with the lone pair of electronegative atoms. The negative (red) regions of MEP were related to electrophilic reactivity and the positive (white) regions to nucleophilic reactivity (Fig. 8). The negative region is localized on the hydrogen atoms and the positive region is

Table 7 Thermodynamic properties for 3DCNDPC obtained by B3LYP/6-311++G(d,p) method. Temp. (K) 100 200 298.15 300 400 500 600 700 800 900 1000 S0 m (J/mol K) 335.73 430.3 512.07 513.54 589.14 658.18 721.32 779.21 832.46 881.66 927.35 C0 p;m (J/mol K) 104.98 175.43 236.47 237.52 288.78 329.94 362.44 388.24 409.09 426.29 440.75 H0 m (kJ/mol) 6.77 20.82 41.12 41.56 67.96 98.98 133.66 171.24 211.14 252.94 296.31

1 For interpretation of color in Fig. 8, the reader is referred to the web version of this article.

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165

Fig. 7. The atomic orbital composition of the frontier molecular orbital of 3DCNDPC.

localized on the nitrogen atom. These results provide information concerning the region where the compound can interact intermolecular and bond metallically. Therefore, Fig. 8 conrms the nonexistence of intermolecular interactions within the molecule. Mulliken population analysis The natural population analysis of title molecule obtained by Mulliken [48] population analysis using B3LYP 6-311++G(d,p) method. Mulliken atomic charge calculation has an important role for the application of quantum chemical calculation of the molecular system. Atomic charge affects dipole moment, polarizability, electronic structure and other molecular properties as the system. The calculated Mulliken charge values of title molecule are listed in Table S1. The results can, however, better represent in illustrate

form as given Fig. 9. It is clearly shown that the carbon atom (C4) has more negative charge whereas all the hydrogen atoms have the positive charges. The positive charge of carbon is found C1, C3, C18 in our compound. The CL13 atom has more positive charge than the other atoms. Nitrogen and Oxygen atom has negative charges. The result suggests that the atoms bonded to O, CL atom and C atoms are electron acceptor and the charge transfer takes place from N to C due to electron accepting substitutions at that position in title molecule. Hyperpolarizability calculations Density functional theory has been used as an effective method to investigate the organic NLO materials. Recent research works have illustrated that the organic non-linear optical materials are

Fig. 8. MEP map of title compound.

Fig. 9. Correlation graphs of thermodynamic properties at different temperature of the title compound.

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having high optical non-linearity than inorganic materials [49]. The rst order hyperpolarizability (btotal) of the title compound 3DCNDPC along with related properties (l, a0 and a) are calculated by using DFTB3LYP method with 6-311++G(d,p) basis set. From the computed tensorial components, b is the calculated for the title compound by taking into account the Kleimman symmetry relations and square of the Cartesian expression for the b tensor [50]. The total static dipole moments l, the mean polarizability a0, the anisotropy of the polarizability a and the mean rst hyper-polarizability b, using the x, y and z components they are dened as: The total static dipole moment is
2 2 l l2 x ly lz

increase of temperature from 100 K to1000 K, which is attributed to the enhancement of the molecular vibration while the temperature increases because at a constant pressure (db = 1 atm) values
0 0 of C 0 p;m , Sm , and Hm are equal to the quantity of temperature [52]. The correlations between these thermodynamic properties and temperatures are tted by quadratic formulas as follows and corresponding tting factors (R2) for these thermodynamic properties are found to be 1, 0.999 and 0.999 for heat capacity, entropy, and enthalpy, respectively. The temperature dependence correlation graphs are shown in Fig. S1. Scale factors have been recommended [53] for an accurate prediction in determining the zero-point vibration energies, heat capacities, entropies, enthalpies.

1=2

The isotropic polarizability is

C 0 p; m 0:166 0:009T 0:000T 2 104 ; S0 m 6:161 0:044T 0:000T 2 104 ; H0 m 4:709 0:044T 0:000T 2 104 ; i1=2

R2 1 R2 0:999 R2 0:999

a0

axx ayy azz 3 h

The polarizability anisotropy invariant is

a 21=2 axx ayy 2 ayy azz 2 azz axx 2 6a2 xx

And the average hyperpolarizability is

 1=2 2 2 b0 b2 x by bz
and

All these thermodynamic data provide helpful information for further study on 3DCNDPC. They can be used to compute the other thermodynamic parameters according to relationships of thermodynamic functions and to determine the directions of chemical reactions according to the second law of thermodynamics in Thermochemical eld [54]. Notice: all the thermodynamic calculations were done in gas phase and they could not be used in solution. Conclusion In the present work, the optimized molecular structure, thermodynamic and electronic properties, vibrational frequencies, intensity of vibrations of the title compound are calculated by DFT method using B3LYP/6-311++G(d,p) basis set. The vibrational FT-IR and FT-Raman spectra of the title compound are recorded and on the basis of agreement between the calculated and experimental results, the assignments of all the fundamental vibrational modes of the title compound are made unambiguously based on the results of the PED output obtained from normal coordinate analysis. The inuence of NH2 group is the electron-withdrawing nature of Cl atom in 3DCNDPC which is also discussed. NBO results reect that the charge transfer is mainly due to NAC group. HOMO and LUMO energy gap explains the eventual charge transfer interactions taking place within the molecule. The stabilization energies have been calculated from second order perturbation theory. The predicted NLO properties of title compound are much greater than those of urea. Mulliken atomic charge analysis shows that charge transfer occurring within the molecule. Thermodynamic properties in the range from 100 K to 1000 K are obtained. The gradients of 0 0 C0 p;m , Sm , H m , and vibrational intensity increases with increase of temperature. 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 material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.saa.2014.02.066. References
[1] H.C. Rodgers, A.J. Knox, Eur. Respir. J. 17 (6) (2001) 13141321.

bx bxxx bxyy bxzz by byyy bxxy byzz bz bzzz bxxz byyz

Since the value of the polarizability (a0) and hyperpolarizability (b0) components of GAUSSIAN 09W output are reported in atomic units (a.u.). The calculated values have been converted into electrostatic units (esu) (a: 1 a.u. = 0.1482 1024 esu, b: 1 a.u. = 8.6393 1030 esu). In our present study, the total static dipole moment, polarizabilities and rst order hyper-polarizabilities of 3DCNDPC were calculated. The calculated self-consistent eld (SCF) energy of 3DCNDPC is 1152.4277 kJ mol1. Table S2 lists the values of the electric dipole moment (Debye) and dipole moment components, polarizabilities and hyperpolarizabilities of the 3DCNDPC. In addition to the isotropic polarizabilities and polarizabilities anisotropy invariant were also calculated. The calculated rst hyperpolarizability and the total molecular dipole moment of title molecule is 7.688429 1030 esu and 1.660 D respectively, obtained by B3LYP/6-311++G(d,p) method gives higher value comparing to the literature [51]. The computed value of rst order hyperpolarizability of 3DCNDPC, which is 20 times greater than that of urea. Based on these facts, it could be concluded that the present material has a reasonably good propensity for nonlinear optical activity. Thermodynamic properties The total energy of a molecule is the sum of translational, rotational, vibrational and electronic energies, i.e., E = Et + Er + Ev + Ee. The statistical thermo chemical analysis of 3DCNDPC is carried out considering the molecule to be at room temperature of 298.15 K and one atmospheric pressure. On the basis of vibrational analysis and statistical thermodynamics, the standard thermody    0 namic functions: heat capacity C 0 p;m , entropy Sm , and enthalpy   H0 were obtained and listed in Table S3. As is evident from m
0 0 Table S3, all the values of C 0 p;m , Sm , and Hm increases with the

S. Sakthivel et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 157167 [2] Lofng, Johannes, Kaissling, Brigitte, Am. J. Physiol. Renal. Physiol. 284 (4) (2003) F628F643. [3] S. Matalon, D.J. Benos, R.M. Jackson, Am. J. Physiol. 271 (1996) L1L22. [4] D.J. Benos, M.S. Awayda, I.I. Ismailov, J.P. Johnson, J. Membr. Biol. 143 (1995) 1 18. [5] H. Garty, D.J. Benos, Physiol. Rev. 68 (2) (1988) 309373. [6] J.G.F. Reynolds, Extra Pharmacopoeia, 29th ed., The Pharmaceuticals Press, London, 1989. pp. 977978. [7] C.G. Kim, V. Lemaitve, A. Watts, W.B. Fischer, Anal. Bioanal. Chem. 386 (2006) 22132217. [8] H. Knauf, K. Reuter, E. Mutscher, Eur. J. Clin. Pharm. 28 (1985) 6166. [9] C.F. George, Br. J. Clin. Pharm. 9 (1980) 495. [10] I. Ramzia, El. Bagary, F. Ehab, Elkady, A. Jabbar Faqeh, J. Chem. Pharm. Res. 3 (2011) 320329. [11] N.C. Handy, C.W. Murray, R.D. Amos, J. Med. Chem. 97 (1993) 43924396. [12] P.J. Stephens, F.J. Derlin, C.F. Charalowski, M.F. Frisch, J. Phys. Chem. 98 (1994) 1162311627. [13] F.J. Delvin, J.W. Finley, P.J. Stephens, M.J. Frish, J. Phys. Chem. 99 (1995) 16883 16902. [14] S.Y. Lee, B.H. Boo, Bull. Korean J. Chem. Soc. 17 (1996) 760764. [15] G. Rauhut, P. Pulay, J. Phys. Chem. 99 (1995) 30933100. [16] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision C.02, Gaussian Inc., Wallingford, CT, 2004. [17] A. Frisch, A.B. Nielson, A.J. Holder, GAUSS VIEW Users Manual, Gaussian Inc., Pittsburgh, PA, 2000. [18] G. Rahght, P. Pulay, J. Phys. Chem. 99 (1995) 30933100. [19] P. Pulay, G. Fogarasi, G. Pongor, J.E. Boggs, A. Vargha, J. Am. Chem. Soc. 105 (1983) 70377047. [20] G. Fogarasi, X. Zhou, P.W. Taylor, P. Pulay, J. Am. Chem. Soc. 114 (1992) 8191 8201. [21] T. Sundius, J. Mol. Struct. 218 (1990) 321326. [22] G. Keresztury, S. Holly, J. Varga, G. Besenyei, A.Y. Wang, J.R. Durig, Spectrochim. Acta A 49 (1993) 20072026. [23] G. Keresztury, in: J.M. Chalmers, P.R. Grifth (Eds.), Raman Spectroscopy: Theory in Handbook of Vibrational Spectroscopy, vol. 1, John Wiley & Sons Ltd., New York, 2002.

167

[24] E.D. Glendening, A.E. Reed, J.E. Carpenter, F. Weinhold, NBO Version 3.1, TCI, University of Wisconsin, Madison, 1998. [25] X.-H. Li, R.-Z. Zhang, X.-Z. Zhang, Struct. Chem. 20 (2009) 10491054. [26] J. Chocholousova, V. Vladimin Spirko, P. Hobza, Phys. Chem. 6 (2004) 3741. [27] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899926. [28] T.A. Halgren, J. Comput. Chem. 17 (56) (1996) 490519. [29] A. Pretscher, M. Brisander, A. Bayerbrandal, L.K. Hangen, Acta Cryst. 57 (2001) 2171219. [30] M. Szafran, A. Komasa, E.B. Adamska, J. Mol. Struct. (Theochem.) 827 (2007) 101107. [31] S. Sebastin, N. Sundaraganesan, Spectrochim. Acta A 75 (2010) 941952. [32] P. Pulay, G. Fogarasi, F. Pang, J.E. Boggs, J. Am. Chem. Soc. 101 (1979) 2550 2560. [33] Y. Wang, S. Saebar, C.U. Pittman Jr., J. Mol. Struct. Theochem. 281 (1993) 86 91. [34] A. Altun, K. Glck, M. Kumru, J. Mol. Struct. Theochem. 637 (2003) 155169. [35] K.B. Wiberg, A. Shrake, Spectrochim. Acta A 29 (1973) 583587. [36] G. Varsanyi, Vibrational Spectra of Benzene Derivates, Academic Press, New York, 1969. [37] M. Szafran, A. Komasa, E.B. Adamska, J. Mol. Struct. THEOCHEM 827 (2007) 101110. [38] M. Arivazhagan, S. Jeyavijayan, Spectrochim. Acta A 79 (2011) 376383. [39] J. Swaminathan, M. Ramalingam, N. Sundaraganesan, Spectrochim. Acta 71A (2009) 17761782. [40] L.J. Bellamy, The Infrared Spectra of Complex Molecules, Wiley, New York, 1959. [41] T. Shimanouchi, Y. Kakiuti, I. Gamo, J. Chem. Phys. 25 (1956) 12451251. [42] D. Sajan, J. Binoy, I.H. Joe, V.S. Jayakumar, Jacek Zaleski, J. Raman Spectrosc. 36 (2005) 221236. [43] M. Gussoni, C. Castiglioni, J. Mol. Struct. 521 (2000) 118. [44] N.M. O Boyle, A.L. tenderholt, K.M. langer, J. Comput. Chem. 29 (2008) 839 845. [45] E. Scrocco, J. Tomasi, Adv. Quant. Chem. 11 (1978) 95115. [46] E.J. Luque, J.M. Lopez, M. Orozco, Theor. Chem. Acc. 103 (2000) 343350. [47] P. Politzer, P.R. Laurence, K. Jayasuriya, Environ. Health Perspect. 61 (1985) 1019. [48] R.S. Mulliken, J. Chem. Phys. 23 (1995) 18331840. [49] N.B. Singh, O.P. Singh, N.P.S.N. Singh, Y.P. Singh, N.B. Singh, Prog. Cryst. Growth Charact. 44 (169) (2002) 169174. [50] D.A. Kleinman, Phys. Rev. 126 (1962) 19771979. [51] P.B. Nagabalasubramanian, S. Periandy, Spectrochim. Acta A 77 (2010) 1099 1107. [52] F. Bopp, J. Meixner, J. Kestin, in: Thermodynamics and Statistical Mechanics, fth ed., Academic Press Inc. (London) Ltd., New York, 1967. [53] G. Varsanyi, P. Sohar, Acta Chim. Acad. Sci. Hung. 74 (1972) 315333. [54] R. Zhang, B. Dub, G. Sun, Y. Sun, Spectrochim. Acta A 75 (2010) 11151124.