Journal of Molecular Structure 1005 (2011) 202213

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Journal of Molecular Structure

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Rotational isomers, vibrational assignments, HOMOLUMO, NLO properties and molecular electrostatic potential surface of N-(2 bromoethyl) phthalimide
T. Karthick a, V. Balachandran b,, S. Perumal c, A. Nataraj d
a

Department of Physics, Vivekanandha College for Women, Tiruchengode 637 205, India Department of Physics, AA Government Arts College, Musiri, Tiruchirappalli 621 201, India c Department of Physics, ST Hindu College, Nagercoil 629 002, India d Department of Physics, Thanthai Hans Roever College, Perambalur 621 212, India
b

a r t i c l e

i n f o

a b s t r a c t
The stable isomer of N-(2 bromoethyl) phthalimide (NBEP) is determined. FT-IR (4000400 cm1) and FT-Raman (3500100 cm1) spectra were recorded on the solid phase of the molecule. Optimized geometrical parameters, vibrational wavenumbers of the stable isomer of NBEP are predicted by DFT/ B3LYP/6-311++G(d,p). Reliable vibrational assignments associated with this molecule is made on the basis of total energy distribution (TED) results. The non-linear optical properties such as dipole moment, polarizability and rst order hyperpolarizability of the title molecule are determined. Density plots over the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) energy surface directly identies the donor and acceptor atoms in the molecule. It also provides information about the charge transfer within the molecule. To obtain chemical reactivity of the molecule, the molecular electrostatic potential (MEP) surface map is plotted over the optimized geometry of the molecule. Furthermore, reactive electrophilic and nucleophilic sites in the MEP surface are compared with the tting point charges to electrostatic potential. Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.

Article history: Received 24 July 2011 Received in revised form 26 August 2011 Accepted 26 August 2011 Available online 16 September 2011 Keywords: Isomers N-(2 bromoethyl) phthalimide DFT Vibrational spectra HOMOLUMO Hyperpolarizability

1. Introduction Phthalimide and its N-substituted phthalimide analogues has been the subject of todays research for many reasons. Owing to their intense applications in pharmacy, medicinal chemistry and industry, vibrational analysis of N-substituted phthalimide derivatives have been investigated earlier. Krishnakumar et al. [1,2] reported the vibrational assignments of N-bromophthalimide and N-hydroxyphthalimide based on DFT theory calculations respectively. In pharmaceutical, they are being used as an intermediate material. In medical eld, phthalimide analogues are being used in the synthesis of antimicrobial activity, androgens and other agents for treating tumor necrosis factor [1]. Apart from their well recognized applications in pharmaceutical, phthalimide analogues play a vital role as anti-convulsant, anti-inammatory, analgesic, hypolipidimic and immunomodulatory activities [3] in medicinal chemistry. Certain phthalimide derivatives are used as herbicides and for reducing bacterial contamination. In industry, they are being widely used in the production of pesticides, dyes, plastics, high performance ion exchange resins, surfactants. In particular, N-(2 bromoethyl) phthalimide (abbreviated as NBEP) is being most extensively used as an
Corresponding author. Tel.: +91 431 2432454; fax: +91 4326 262630.
E-mail address: brsbala66@gmail.com (V. Balachandran).

intermediate material for the synthesis of a drug [4]. The understanding of molecular geometry, vibrational analysis as well as delocalization of charges, reactive electrophilic and nucleophilic sites of the compound have special attention in the synthesis of a drug and it is the subject of todays experimental and theoretical studies. Hence in the present study, the energies of different possible rotational isomers are determined. The optimized geometrical parameters, vibrational assignments, certain non-linear optical properties (such as, dipole moment, polarizability, and hyperpolarizability) and HOMOLUMO energy gap for the title molecule are analyzed. Moreover, molecular electrostatic potential (MEP) surface is plotted over the optimized geometry to elucidate the reactivity of NBEP molecule. To the best of our knowledge, neither vibrational assignments nor hyperpolarizability, HOMOLUMO energy calculations have ever been made on the basis of N-(2 bromoethyl) phthalimide. This inadequacy observed in the literature encouraged us to make vibrational spectroscopic studies, non-linear optical properties and HOMOLUMO energy calculations on NBEP. 2. Methodology 2.1. General The sample NBEP in the solid form was purchased from the Lancaster Chemical Company, (UK) with a purity of greater than

0022-2860/$ - see front matter Crown Copyright 2011 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2011.08.051

T. Karthick et al. / Journal of Molecular Structure 1005 (2011) 202213

203

98% and it was used as such without further purication. The FT-IR spectrum of NBEP is recorded in the wavenumber region 400 4000 cm1 on a NEXUS 670 spectrophotometer equipped with an MCT detector, a KBr pellet technique. The FT-Raman spectrum of NBEP is recorded in the wavenumber region 1003500 cm1 on a NEXUS 670 spectrophotometer equipped with Raman module accessory. The Nd:YAG laser of wavelength 1064 nm operating at 1.5 W power is used as an excitation source.

3.2. Optimized structure parameters The optimized conguration corresponding to the stable isomer of NBEP given in Fig. 2 has 22 atoms which belong to N-substituted heterocyclic aromatic organic compound. The optimized geometrical parameters of NBEP calculated at B3LYP/6-311++G(d,p) level are presented in Table 2. Since the exact crystal structure of the title compound is not available till now, the optimized geometrical parameters are compared with the available experimental data of similar kind of molecules [1]. It is observed that, CAC bond lengths in the optimized geometry of NBEP fall in the range: 1.38521.3990 for six member ring. Introduction of substituent in the N-substituted phthalimide ring leads to signicant variation in charge distribution in the molecule. Consequently, this greatly affects the molecular geometrical parameters of the ve member ring. Hence, the CAC bond lengths of the ve member ring such as C1AC8 (1.4920 ), C3AC9 (1.4925 ) are distorted and appear somewhat longer than that of aromatic ring. The calculated CAC bond lengths of six and ve member ring of NBEP are found to be in good agreement with the experimental bond lengths of phthalimide and N-bromophthalimide [1]. Due to the inuence of bromoethyl substituent on N-substituted phthalimide, the interatomic distance N2AC11 (1.4536 ) is slightly differ from N2AC3 (1.4097 ) and C1AN2 (1.4022 ). The average CAH bond length in the aromatic ring calculated by B3LYP/6-311++G(d,p) is $1.0836 whereas outside the ring; the average CAH bond length (1.0902 ) is found to be large when compared to aromatic CAH. It is also observed that, C14ABr17 bond length is calculated as 1.9762 . The C@O bond lengths such as C1AO10 and C3AO18 calculated by B3LYP/6-311++G(d,p) are very closer to the experimental data. Due to the symmetry of the benzene ring, its bond angles are almost equal. Therefore, the average bond angle corresponding to aromatic CACAH calculated at B3LYP/6-311++G(d,p) is 120.44. In the ve member ring, the average CACAO bond angle (C8AC1AO10, C9AC3AO18) calculated is 128.76. As far as the title molecule is concerned, variation in bond angle is not appreciable. In other words, the substituent does not affect bond angle of phthalimide ring signicantly. From the theoretical values, we found most of the optimized bond lengths are in good agreement with experimental bond lengths but bond angles are slightly longer and shorter than that of experimental values. 3.3. Normal coordinate analysis There are 60 fundamental modes of vibrations associated with this title molecule. In agreement with C1 symmetry, all the 60 vibrations are distributed as 41 in-plane and 19 out-of-plane vibrations of same symmetry species. A detailed description of the vibrational modes can be given by means of normal coordinate analysis (NCA). For this purpose, the full sets of 83 standard internal coordinates [containing 23 redundancies] are dened as given in the Table 3. From the full set of 83 internal co-ordinates, a nonredundant set of local symmetry coordinates are constructed by means of suitable linear combinations of internal coordinates followed by the recommendations of Fogarasi and Pulay [12,13]. The local symmetry co-ordinates corresponding to probable degrees of freedom of NBEP are presented in Table 4. 3.4. Hyperpolarizability and HOMOLUMO energy gap Based on the nite-eld approach, the non-linear optical parameters such as dipole moment, polarizability, anisotropy polarizability and rst order hyperpolarizability of NBEP molecule are calculated using B3LYP method with basic function set 6311++G(d,p) for more reliability. The numerical values of above

2.2. Computational details In order to obtain stable isomer, the self consistent eld (SCF) energy calculation is performed on the possible rotational isomers of NBEP using B3LYP method with basic function set 6-311++G(d,p) for better results. In the present study, the entire optimized geometrical and vibrational parameters for the stable isomer of NBEP are predicted by means of Density Functional B3LYP method with internally stored standard 6-311++G(d,p) basis set level in Gaussian 03 W software package [5]. B3LYP represents Beckes three-parameter hybrid functional method [6] with Lee YangParrs correlation functional (LYP) [7,8]. In the calculations, the electronic structure of NBEP in the ground state is optimized by assuming C1 point group symmetry and the charge of each point is taken as zero and the spin multiplicity is taken as one. Because of the neglect of anharmonicity effect at the beginning of calculation, the predicted vibrational wavenumbers at B3LYP/6-311++G(d,p) method are found to be in disagreement with experimental wavenumbers. In order to bring the calculated wavenumber closer to that of experimental, two different empirical scaling factors are introduced. Reliable vibrational mode assignments made in this work are performed on the basis of total energy distribution (TED) results obtained from MOLVIB program (version V7.0-G77) written by Sundius [911]. The non-linear optical properties such as dipole moment, polarizability, and rst order hyperpolarizability of NBEP are computed with the aid of B3LYP/6-311++G(d,p) levels of DFT theory. The frontier molecular orbital energies, energy gap between various occupied and unoccupied molecular orbitals of NBEP are also calculated in the same method. For obtaining chemical reactivity of the molecule, molecular electrostatic potential (MEP) surface is plotted over the optimized geometry of stable isomer of NBEP using Gaussian 03W software package [5]. The tting point charges to the electrostatic potential on each atom of the optimized geometry are compared with MEP surface. Moreover, certain thermodynamic properties such as entropy, enthalpy, rotational, vibrational constants, and zero point vibrational energy of the title compound are also calculated at the same level of DFT theory.

3. Results and discussion 3.1. Rotational isomers To obtain stable isomer geometry, the self consistent eld (SCF) energy calculation is performed on the nine possible isomers of NBEP as shown in Fig. 1. The possibility of isomer geometry is found by locating ACH2Br group of the title molecule in three different orientations. The position of Br atom in different orientations gives rise to nine possible isomers. The SCF energy calculation reveals that, the isomer f acquires dominant stability among others as shown in Table 1. It is also observed that, the energy of the isomer e is almost equal to that of f isomer and conformer g possesses least stability.

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Fig. 1. Possible rotational isomer geometry of N-(2 bromoethyl) phthalimide.

Table 1 Calculated energies and energy difference for Possible rotational isomers of N-(2 bromoethyl) phthalimide by B3LYP/6-311++G(d,p) method. Rotational isomers a b c d e f g h i Energy (kJ/mol) 8310551.436 8308726.681 8310554.170 8310532.639 8310561.050 8310561.052 8308720.962 8310554.115 8310551.381 Energy differencesa (kJ/mol) 9.616 1834.371 6.882 28.413 0.002 0.000 1840.09 6.937 9.671

a Energies of the other eight possible isomers relative to the most stable (f) conformer.

Fig. 2. Stable isomer geometry of N-(2 bromoethyl) phthalimide.

mentioned parameters are listed in Table 5. In the presence of an external electric eld (E), the energy of the system is a function of the electric eld. First hyperpolarizability is a third-rank tensor that can be described by a 3 3 3 matrix. The 27 components of the 3D matrix can be reduced to 10 components because of the Kleinman symmetry [14]. The components of b are dened as the coefcients in the Taylor series expansion of energy in an external electric eld. When an external electric eld is weak and homogeneous, Taylor series expansion becomes

where E is the energy of the unperturbed molecules, Fi is the eld at origin and li, aij, bijk and c ijkl are the components of dipole moment, polarizability, rst hyperpolarizabilities and the second hyperpolarizabilities, respectively. The total static dipole moment l, mean polarizability a0, anisotropy of the polarizability Da and rst hyperpolarizability btot using x, y and z mponents, are dened as

l l2 l2 l2 1=2 x y z
a0
axx ayy azz 3

E E0

li F i
1!

aij F i F j
2!

bijk F i F j fk cijkl F i F j F k F l 3! 4!

T. Karthick et al. / Journal of Molecular Structure 1005 (2011) 202213 Table 2 Optimized bond lengths and bond angles of N-(2 bromoethyl) phthalimide obtained at B3LYP/6-311++G(d,p) method. Parametersa Bond length () Experimentalb Ph C1AN2 C1AC8 C1AO10 N2AC3 N2AC11 C3AC9 C3AO18 C4AC5 C4AC9 C4AH19 C5AC6 C5AH20 C6AC7 C6AH21 C7AC8 C7AH22 C8AC9 C11AH12 C11AH13 C11AC14 C14AH15 C14AH16 C14ABr17 1.4022 1.4920 1.4206 1.4097 1.4536 1.4925 1.4268 1.3990 1.3852 1.0833 1.3989 1.0839 1.3989 1.0839 1.3853 1.0833 1.3938 1.0962 1.0903 1.5222 1.0861 1.0880 1.9762 1.40 1.45 1.42 1.40 N-BrPh 1.35 1.53 1.43 1.35 N2AC1AC8 N2AC1AO10 C8AC1AO10 C1AN2AC3 C1AN2AC11 C3AN2AC11 N2AC3AC9 N2AC3AO18 C9AC3AO18 C5AC4AC9 C5AC4AH19 C9AC4AH19 C4AC5AC6 C4AC5AH20 C6AC5AH20 C5AC6AC7 C5AC6AH21 C7AC6AH21 C6AC7AC8 C6AC7AH22 C8AC7AH22 C1AC8AC7 C1AC8AC9 C7AC8AC9 C3AC9AC4 C3AC9AC8 C4AC9AC8 N2AC11AH12 N2AC11AH13 N2AC11AC14 H12AC11AH13 H12AC11AC14 H13AC11AC14 C11AC14AH15 C11AC14AH16 C11AC14ABr17 H15AC14AH16 H15AC14ABr17 H16AC14ABr17 105.74 125.01 129.25 112.13 124.02 123.80 105.42 125.35 129.22 117.40 121.63 120.97 121.08 119.58 119.35 121.07 119.35 119.58 117.40 121.60 121.00 130.20 108.27 121.53 130.07 108.41 121.52 108.79 106.62 114.19 108.58 107.37 111.18 111.97 110.03 112.76 110.07 105.98 105.79 Parametersa Bond angle () Experimentalb Ph 108.23 125.80 125.85 110.37

205

N-BrPh 108.23 125.94 125.91 110.34

1.43 1.38 1.09 1.39 1.10 1.40 1.38 1.09 1.44

1.43 1.34 1.07 1.41 1.06 1.41 1.34 1.06 1.35

125.80

125.80

121.34 121.34

121.35 121.35

117.27

117.37

122.91 130.54

123.15 130.42

a b

For numbering of atom see Fig 1. Ref. [1].

h i1=2 Da 21=2 axx ayy 2 ayy azz 2 azz axx 2 6a2 xz btot b2 b2 b2 1=2 x y z
and

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

The B3LYP/6-311++G(d,p) method calculated the rst hyperpolarizability of NBEP is 0.09636 1031 esu. The total molecular dipole moment (l), mean polarizability (a0) and anisotropy polarizability (Da) of NBEP molecule are collected in Table 5. While comparing hyperpolarizability of molecules reported earlier [15,16], the numerical value of rst hyperpolarizability of this molecule is not appreciable. In other words, the title molecule NBEP has less non-linear optical response. Hence we conclude that, the title molecule is not suitable for future non-linear optical studies. Fig. 3 shows mapped isodensity surface plots of molecular orbitals from HOMO 2 to LUMO + 2 of the title molecule in which all the LUMO surfaces are well localized within the phthalimide ring. In other words all the ring component intramolecular interactions

mostly occurred in LUMO levels. It is also observed that, all the surfaces shown in Fig. 3b, d, and f have no amplitude [17] on ethyl group linked to the ve member ring of NBEP. In contrast, all the mapped HOMO surfaces shown in Fig. 3a, c, and e are well localized on the ethyl group. In this case, the orbital overlapping within the phthalimide ring is absent except HOMO 2. In HOMO 2, C14 in ethyl group is highly coupled with H15, H16 and Br17. The presence of orbital overlapping within the molecule reveals that, there is an intramolecular interaction exists between bonding (p) and antibonding (p) molecular orbitals. The presence of intramolecular charge transfer from donor to acceptor group within molecule can also be identied by analyzing the co-existence of IR and Raman activity [16] itself. It is also observed that in our title molecule the bands at 2975, 1725, 1433, 732, 604 and 585 cm1 in FT-IR spectrum have their counterparts in FT-Raman at 2978, 1725, 1428, 730, 607 and 583 cm1. This shows that the relative intensities in IR and Raman are comparable resulting from the electron cloud movement through single-double bond p conjugated path from donor to acceptor groups. The analysis of wave function indicates that, the electron absorption corresponding to the transition from the ground state to the rst exited state is mainly described by one-electron excitation from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The HOMO, LUMO energies of stable isomer of NBEP calculated at B3LYP/6-311++G(d,p) level are pre-

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Table 3 Denition of internal coordinates associated with N-(2 bromoethyl) phthalimide. No(i) Stretching 14 56 79 10 11 1219 2023 Symbol ri Ri ti Xi Pi Pi ri Type CAH (aromatic) C@O CAN CABr CAC (ethylene) CAC (aromatic) CAH (ethylene) CACAH CACAO NACAO CANAC t(Ring 1) t(Ring 2) NACAH (ethylene) HACAH CACAH (ethylene) HACABr CarAH C@O CAN t(N)ACH2 t(Ring1) t(Ring2) Buttery NACACAH NACACAX
a

Denition

C4AH19, C5AH20, C6AH21, C7AH22 C1AO10, C3AO18 C1AN2, C3AN2, C11AN2 C14ABr17 C11AC14 C4AC5, C5AC6, C6AC7, C7AC8, C8AC9, C9AC4, C9AC3, C8AC1 C11AH12, C11AH13, C14AH15, C14AH16 C9AC4AH19, C5AC4AH19, C4AC5AH20, C6AC5AH20, C5AC6AH21, C7AC6AH21, C6AC7AH22, C8AC7AH22 C9AC3AO18, C8AC1AO10 N2AC3AO18, N2AC1AO10 C3AN2AC11, C1AN2AC11 C4AC5AC6, C5AC6AC7, C6AC7AC8, C7AC8AC9, C8AC9AC4, C9AC4AC5 C1AC8AC9, C8AC9AC3, C9AC3AN2, C3AN2AC1, N2AC1AC8 N2AC11AH12, N2AC11AH13 H12AC11AH13, H15AC14AH16 C11AC14AH15, C11AC14AH16 H15AC14ABr17, H16AC14ABr17 H19AC4AC5AC9, H20AC5AC6AC4, H21AC6AC7AC5, H22AC7AC8AC6 O10AC1AC8AN2, O18AC3AC9AN2 C11AN2AC3AC1 C1AN2AC11AH12, C1AN2AC11AH13, C3AN2AC11AH12, C3AN2AC11AH13 C4AC5AC6AC7, C5AC6AC7AC8, C6AC7AC8AC9, C7AC8AC9AC4, C8AC9AC4AC5, C9AC4AC5AC6 C8AC1AN2AC3, C1AN2AC3AC9, N2AC3AC9AC8, C3AC9AC8AC1, C9AC8AC1AN2 C7AC8AC9AC3, C4AC9AC8AC1 N2AC11AC14AH15, N2AC11AC14AH16 N2AC11AC14ABr17

In-plane bending 2431 bi 3233 /i 3435 pi 3637 ri 3843 bi 4448 bi 4950 wi 5152 wi 5354 bi 5556 wi Out-of plane bending 5760 xi 6162 xi 63 qi 6667 di 6873 si 7478 si 7980 si 8182 xi 83 xi
a

For numbering of atom see Fig 1.

sented in Table 6. The energy gap presented in Table 6 reects the chemical activity of the molecule. HOMO represents the ability to donate an electron and LUMO represents the ability to accept an electron. Among the six subsequent excited states calculated, the strongest transition appears between HOMO ? LUMO orbitals. The numerical value of energy gap between HOMOLUMO orbitals calculated at B3LYP level is 0.18393 a.u. The energy gaps for other possible energy transitions are also presented in Table 6.

3.5. Molecular electrostatic potential Molecular electrostatic potential (MEP) at a point in space around a molecule gives information about the net electrostatic effect produced at that point by total charge distribution (electron + proton) of the molecule [18]. Moreover, MEP surface helps to predict the reactivity of wide variety of chemical systems in both electrophilic and nucleophilic reactions, the study of biological recognition processes and hydrogen bonding interactions [19,20]. It also provides visual understanding of relative polarity of the molecule. An electron density isosurface mapped with electrostatic potential surface depicts the size, shape, charge density and reactive sites of the molecules. The different values of the electrostatic potential at the surface are represented by different colors; red represents regions of most electro negative electrostatic potential, blue represents regions of most positive electrostatic potential and green represents regions of zero potential. The electrostatic potential increases in the order red < orange < yellow < green < blue [18]. To predict reactive sites for electrophilic and nucleophilic attack for the investigated molecule, MEP surface is plotted over optimized geometry of stable isomer of NBEP at B3LYP/6311++G(d,p) basis set. Fig. 4 (left) shows electrostatic potential contour map of NBEP along with the tting point charges to the electrostatic potential (see the right side of Fig. 4), where the elec-

tron density isosurface being 0.02 a.u. In the present study, the value of point charges to the electrostatic potential are predicted with the help of B3LYP level of the theory incorporating 6311++G(d,p) basis set. As easily can be seen in Fig. 4, investigated molecule has several possible sites for electrophilic (the electrophilic sites are most electro negative and are represented as red color) and nucleophilic attack (the nucleophilic sites are most positive and are represented as blue color). The tting point charge to the electrostatic potential indicates that, the atom O10 and O18 are the most electronegative (0.5606 e) atoms in NBEP molecule. The calculated point charge corresponding to N2 atom is 0.1479 e. But, the region very close to N2 appears blue color in MEP surface. This is because of the fact of that, N2 atom of NBEP is surrounded by most electropositive atoms (C3 = 0.4400, C3 = 0.3697 and C11 = 0.2021 e). From this gure, we also found that charges accumulated on hydrogen atoms of the ring and ethyl groups are less positive, while ring carbon atoms such as C9 (0.0399 e), C4 (0.1026 e), C5 (0.1268 e) and C6 (0.1324 e) are less negative. The uniform charge distributions on the ring components protect the symmetry of six member ring from substituent. It is also seen in Fig. 4 that, the region of less electro positive (yellow color) envelops the p-system of benzene ring, which prevent the ring hydrogen atom from more electrophilic region.

3.6. Vibrational spectra Usually harmonic wavenumbers derived from Gaussian 03 are found to be in disagreement with that of experimental due to the neglect of anharmonicity effect at beginning of calculation, electron correlation approximate treatment and basis set deciencies, etc., [21]. Linear scaling procedure is adopted in this work to eliminate errors in the harmonic wavenumber output. After implementing scaling procedure, the theoretically computed wavenumbers matched well with the experimental ones. Based on this

T. Karthick et al. / Journal of Molecular Structure 1005 (2011) 202213 Table 4 Denition of local symmetry coordinates for N-(2 bromoethyl) phthalimide. No(i) Stretching 14 56 79 10 11 1219 20 21 22 23 Type CHar C@O CN CABr CAC (ethylene) CCar (CH2)1 ss (CH2)1 as (CH2)2 ss (CH2)2 as
a

207

Denition

r1, r2, r3, r4 R5, R6 t7, t8, t9 X10 P11 P12, P13, P14, P15, P16, P17, P18, P19 r20 + r21 r20 r21 r22 + r23 r20 r21 p p b24 b25 = 2; b26 b27 = 2; p p b28 b29 = 2; b30 b31 = 2 p /32 /33 = 2 p p34 p35 = 2 p r36 r37 = 2

In-plane bending 2427 bCH 28 29 30 31 32 33 34 35 36 37 38 49 40 41 42 bCO bCO bCN Ring 1 Ring 2 Ring 3 Ring 4 Ring 5 CH2 scissoring CH2 scissoring CH2 rocking CH2 rocking CH2 twisting CH2 twisting bCABr

p b38 b39 2b40 b41 b42 2b43 = 12 p b38 b39 b41 b42 = 2 b44 ab45 b48 bb46 b47 a bb44 b47 1 ab45 b46 p 2W49 W50 W51 = 6 p 2W53 W54 W52 = 6 p W50 W51 = 2 p W54 W52 = 2 p W50 W51 = 2 p W54 W52 = 2 p W55 W56 = 2

p b38 b39 b40 b41 b42 b43 = 6

Out-off plane bending 4346 xCH 4748 xCO 49 xCN 5051 xNACAH 52 53 54 55 56 57 5859 60 t Ring1 t Ring2 t Ring3 t ring4 t ring5 Buttery CH2 wagging

x57, x58, x59, x60 x61, x62 x63 p p x64 x65 = 2; x66 x67 = 2
s68 s69 s70 s71 s72 p s68 s69 s70 s71 = 2

2975 cm1 in FT-IR and the bands at 3090, 3068, 3020 and 2978 cm1 in FT-Raman are assigned to CAH stretching modes of the ring system. The scaled theoretical values at B3LYP/6311++G(d,p) of ring CAH stretching modes coincide well with that of experimental data as depicted in Table 7. For phthalimide compound, the bands at 3230, 3180, 3095 and 2950 cm1 in FT-IR were assigned to ring CAH stretching modes [1]. For N-bromophthalimide the bands at 3198, 3058, 2936, 2870 cm1 in FT-IR were assigned to ring CAH stretching modes [1]. From these results, we conclude that the vibrational wavenumbers associated with six member ring of phthalimide are greatly affected by the nature of substituents. The percentage of TED predicts that CAH modes of NBEP are very pure since their percentage is almost 100%. However, CAH stretching modes have also been satised harmonic oscillator equation [24]. According to this, vibrational wavenumber is proportional to the root of bond force constant and is inversely proportional to the root of reduced masses of possible pairs of the molecule. As a result, large vibrational wavenumbers will be associated with light atoms. Thus the CAH stretching modes of NBEP appear in the range 30992724 cm1 by B3LYP/6-311++ G(d,p). Average force constants corresponding to CAH stretching modes calculated at B3LYP/6-311++G(d,p) is 6.3539 mdyne/ and average reduced masses for CAH stretching modes of NBEP is 1.08753 amu. The ethyl group of the title molecule gives rise to four stretching modes and the couple of scissoring, wagging, rocking and twisting modes. The peaks for all the four stretching modes are observed in this title region. The band observed at 2913 cm1 in FT-IR and bands at 2910 cm1 in FT-Raman is assigned to asymmetric CAH stretching modes of the ethyl group of NBEP. The very strong band at 2860 cm1 and a weak band at 2720 cm1 in FT-IR are designated as symmetric CAH stretching modes. 3.6.2. Spectral region between 1900 and 1200 cm1 As far as the title compound is concerned, the region 1900 1300 cm1 has very strong and sharp peaks as shown in Figs. 5 and 6. On the basis of TED, the prominent absorptions at 1780, 1725 cm1 in FT-IR and 1775, 1725 cm1 in FT-Raman are assigned to C@O stretching modes. From this we found that, the intensity of these bands in FT-IR is very high. Similarly very large force constants have been reported against C@O stretching vibrations (Table 7). Such intense infrared absorption bands are observed due to the fact that, the multiple bonded carbonyl group is highly polar [25]. The pattern of band observed at 1615, 1328 and 1178 cm1 in FTIR and 1615, 1322 and 1180 cm1 in FT-Raman are assigned as CAC stretching vibrations of the aromatic system (also known as skeletal vibrations) [26]. The scaled theoretical wavenumbers corresponding to skeletal CAC stretching vibrations at B3LYP/6311++G(d,P) level show excellent agreement with those observed experimentally. Beside the CAC skeletal, multiple combinations or overtones are observed in this region in relation to aromatic CAH in-plane bending, CH2 in-plane scissoring and CH2 in-plane wagging of the ethyl group. In the present study, the medium strong band at 1476 cm1 in FT-IR and 1470, 1458 cm1 in FT-Raman are assigned to CAH inplane bending of the six member ring. The percentage of TED for this mode is about 70%. Moreover, the skeletal CAC stretching modes are also taking a crucial part (13%) in these modes (m13, m14) since their TED contributions are 15 and 13%, respectively. For NBEP molecule, the assignment of the skeletal CAC stretching mode in both FT-IR and FT-Raman is quite difcult, since this band is frequently masked by the more intense bands at 1240 1100 cm1 (FT-Raman) arising from the CH2 deformation (H15AC14AH16, H12AC11AH13) vibrations [27,28]. The theoretically calculated CH2 deformation modes have been consistent with the recorded spectral data (Table 7). One of the CH2 deformation

p s73 = 6

p s68 2s69 s70 s71 2s72 s73 = 12 bs74 s78 as75 s77 s76 a bs78 s74 1 as77 s75 p s79 s80 = 2 x81, x82

xCABr

x83

a = cos 144, b = cos 72. a For numbering of atom see Fig. 1.

procedure, the theoretical harmonic wavenumbers have been scaled by the scale factor of 0.958 and 0.983 in the region from 3200 to 1700 cm1 and lower than 1700 cm1, respectively [22]. For comparative purpose, scaled theoretical and experimental FTIR, FT-Raman wavenumbers are summarized in Table 7 along with detailed vibrational assignments and calculated IR intensities and Raman activities. Similarly, the experimental and calculated FT-IR and FT-Raman spectra are also presented in Figs. 5 and 6 for comparative purpose. The title molecule NBEP has 22 atoms and possesses 60 normal vibrational modes, where all such modes are assigned on the basis of total energy distribution results obtained from MOLVIB output. The detailed assignments along with the percentage of TED are summarized in Table 7, where the assignments having <10% (TED percentage) are ignored. 3.6.1. Spectral region between 3200 and 3000 cm1 The characteristic wavenumbers of this region belong to CAH stretching modes [23]. The theoretical description for this region is somewhat difcult due to the weakness of CAH stretching modes. For NBEP, the very weak absorption band at 3095,

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Table 5 Electric dipole moment l (Debye), mean polarizability a0 (1022 esu), anisotropy polarizability Da (1025 esu) and rst hyperpolarizability btot (1031 esu) for N-(2 bromoethyl) phthalimide. Parameters Values 2.8466 0.7474 0.2819 2.9566 1.2842 17.5756 10.8284 0.9857 28.3760 1.0740 1.1012 3.7969 Parameters bxxx byyy bzzz bxyy bxxy bxxz bxzz byzz byyz bxyz btot Values 0.3498 0.3726 0.6623 0.4748 18.9358 0.6724 0.2631 1.8809 0.4663 1.1579 0.09636

lx ly lz l axx axy axz ayy ayz azz a0 Da

The medium strong band at 1370 cm1 in FT-IR is attributed to CH2 wagging (xCH2). The percentage of TED reveals that, all the inplane CH2 deformations are pure modes except mode m20. The assignment of CAN stretching modes is rather difcult task, since there are problems in identifying these wavenumbers from other vibrations. Silverstein et al. [29] assigned the CAN stretching absorption in the region 13821266 cm1 for substituted heterocyclic aromatic compounds. In the present study, CAN stretching modes are assigned on the basis of TED. The observed strong band at 1234 cm1 in FT-IR and the weak bands at 1355, 1232 cm1 in FT-Raman are assigned to CAN stretching modes. The wavenumbers at 1361, 1238 and 1066 cm1 calculated by B3LYP/6311++G(d,p) show excellent agreement with the experimental data. 3.6.3. Spectral region between 1200 and 800 cm1 Most of the in-plane and out-of-plane bending vibrations of ring CAH modes are reported in this region. The bands at 1476, 1257 cm1 in FT-IR and 1470, 1458, 1258 cm1 in FT-Raman are assigned to aromatic CAH in-plane bending vibrations. CAH outof plane vibrations of NBEP are mostly very pure modes. In the present study, the observed bands occur at 985, 875 cm1 in FTIR and 978, 870 cm1 in FT-Raman are designated as ring CAH

modes called CH2 scissoring generates bands at 1433 and 1400 cm1 in FT-IR. In FT-IR spectrum, the bands at 1428 and 1397 cm1 are assigned to CH2 scissoring. The predicted values for CH2 scissoring modes at 1435, 1404 cm1 by B3LYP/6311++G(d,p) are matched well with that of experimental as well as the range given in the literature [1].

(a) HOMO

(b) LUMO

(c) HOMO1

(d) LUMO+1

(e) HOMO2

(f) LUMO+2

Fig. 3. Isodensity plots of the frontier molecular orbitals of N-(2 bromoethyl) phthalimide.

T. Karthick et al. / Journal of Molecular Structure 1005 (2011) 202213 Table 6 Selected HOMO, LUMO energies and their energy gap of N-(2 bromoethyl) phthalimide. S. No 1 2 3 4 5 6 7 8 9 Molecular orbitals HOMO HOMO 1 HOMO 2 LUMO + 2 LUMO + 1 LUMO Energy (a.u) 0.27966 0.28465 0.28741 0.02359 0.06023 0.09859 Molecular orbital energy transitions HOMO ? LUMO HOMO 1 ? LUMO HOMO 2 ? LUMO HOMO ? LUMO + 1 HOMO 1 ? LUMO + 1 HOMO 2 ? LUMO + 1 HOMO ? LUMO + 2 HOMO 1 ? LUMO + 2 HOMO 2 ? LUMO + 2

209

Energy gap (a.u) 0.18107 0.18606 0.18882 0.21943 0.22442 0.22718 0.25607 0.26106 0.26382

C3 C1 H15 H16 C11 H22 H19 H21 H20 C8 H13 H12 C9 C4 Br17 C5 C6 N2 C7 C14 O18 O10

0.4400 0.3697 0.2298 0.2064 0.2021 0.1812 0.1690 0.1647 0.1607 0.0840 0.0836 0.0596 0.0399 0.1026 0.1102 0.1268 0.1324 0.1479 0.1502 0.4383 0.5419 0.5606

Fig. 4. Molecular electrostatic potential (MEP) surface (left) mapping and tting point charges to the electrostatic potential (right) of N-(2 bromoethyl) phthalimide.

out-of plane bending vibrations. The theoretical scaled wavenumbers of these modes are found to be an excellent agreement with the experimental FT-IR and FT-Raman wavenumbers. Like CAN stretching, the CAN bending modes are also coupled with bCHeth and s ring vibrations. In FT-IR, band at 894 cm1 in FT-IR is designated as CAN in-plane bending mode. The percentage of TED contributing to this mode is about 76%. In the present work, a weak intense band at 392 cm1 in FT-Raman is assigned as CAN out-of-plane vibration. The experimental counterpart belongs to cCN in FT-IR is not observed, because cCN vibration is observed only in far IR region. The calculated theoretical wavenumber 396 cm1 depicted in Table 7 is an excellent agreement with the experimental FT-Raman wavenumber. For ethyl moieties of the compound, the peaks at 1205 cm1 in FT-IR and 1205, 1076 cm1 in FT-Raman are ascribed to ethyl twisting vibrations (@CH2). Ethyl rocking vibrations of the title compound display medium strong peak at 807 cm1 in FT-IR and weak bands at 800, 316 cm1 in FT-Raman. The wavenumber of CH2 deformations based on B3LYP/6-311++G(d,p) show better results when comparing experimental CH2 deformations. The C@O

in-plane bending modes are mixed with @CH2, and bCH. The bands at 854, 746 cm1 in FT-IR are assigned to C@O in-plane bending modes. 3.6.4. Spectral region below 800 cm1 The region below 800 cm1 is mostly dominated by in-plane and out-of-plane ring vibrations. In this region, we also expect C@O out-of-plane and CABr vibrations. Usually in-plane ring deformation vibrations are at higher wavenumbers than out-ofplane vibrations [30]. In the present study, the bands observed at 604, 523 cm1 in FT-IR and 710, 700, 607, 525 and 406 cm1 in FT-Raman are assigned to ring in-plane bending modes. The ring out-of-plane bending mode wavenumbers observed in FT-Raman spectra are reported in Table 7. The C@O out-of-plane vibrations are coupled with cCH and are observed at 680 cm1 in FT-IR and 677, 358 cm1 in FT-Raman. The heavier mass of bromine Br17 obviously makes CABr stretching to appear at longer wavelength region (200480 cm1) as reported by Varasanyi [31]. In the present study, stretching mode of CABr is not observed in both FT-IR and FT-Raman. Hence the assignment

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Table 7 Observed and calculated vibrational wavenumbers (cm1), force constants (mdyne/), reduced masses (amu) of N-(2 bromoethyl) phthalimide. Vibrational mode No. Symmetry species Experimental wavenumbers (cm1) FT-IR m1 m2 m3 m4 m5 m6 m7 m8 m9 m10 m11 m12 m13 m14 m15 m16 m17 m18 m19 m20 m21 m22 m23 m24 m25 m26 m27 m28 m29 m30 m31 m32 m33 m34 m35 m36 m37 m38 m39 m40 m41 m42 m43 m44 m45 m46 m47 m48 m49 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A 3095vw 2975s 2913vs 2860vs 2720w 1780s 1725vs 1615vw 1476ms 1433vs 1400ms 1370ms 1328s 1257w 1234s 1205vw 1178vw 1017w 985w 933w 894w 875s 854w 807ms 770w 746w 732s 680w 604s 585s 523ms FTRaman 3090w 3068ms 3020w 2978ms 2910ms 1775vs 1725s 1615s 1470w 1458vw 1428ms 1397vw 1355vw 1322vw 1258w 1232w 1205w 1180w 1076vw 1008s 978vw 938vw 870w 800w 730s 710s 700w 677ms 607ms 583ms 525w 406vw 3210 3197 3186 3175 3156 3117 3095 3029 1826 1771 1687 1628 1516 1500 1485 1473 1427 1397 1381 1343 1309 1278 1228 1209 1192 1180 1104 1093 1043 1026 1010 996 957 928 902 873 821 789 765 749 728 717 692 617 602 537 510 464 417 3099 3072 3025 3010 2980 2917 2866 2724 1782 1730 1619 1552 1478 1462 1435 1404 1374 1361 1330 1296 1262 1238 1211 1185 1169 1154 1079 1066 1023 1012 988 968 940 900 878 856 803 776 751 735 714 703 679 604 588 524 497 452 408 8.8 2.7 5.1 1.1 1.5 0.7 11.6 19.6 102.6 644.4 16.1 2.5 7.0 0.0 13.1 34.6 93.5 259.7 25.6 130.9 1.8 17.9 17.5 13.7 4.6 5.4 9.9 52.6 13.2 16.2 0.0 2.6 23.6 23.1 0.0 10.9 13.9 10.1 0.4 85.1 3.5 5.3 0.1 5.0 12.0 9.9 9.2 0.0 1.5 280.7 31.0 124.0 47.6 59.8 35.9 160.1 188.6 122.1 17.0 35.2 7.6 2.9 2.3 7.7 16.4 14.1 32.4 1.1 18.3 0.2 7.2 39.4 38.4 4.9 8.7 1.5 3.8 6.0 33.1 0.0 0.2 1.2 4.7 0.0 4.5 1.4 1.1 0.2 0.2 11.6 7.0 0.2 11.4 10.8 1.7 9.6 0.1 0.9 1.0967 1.0939 1.0906 1.1094 1.0870 1.0942 1.0602 1.0682 12.4052 12.7363 6.9096 7.1850 2.4088 2.5518 1.0993 1.1154 1.7537 2.6740 5.9707 1.3923 1.5620 1.4004 1.6654 2.7270 2.1450 1.1787 2.0514 1.9540 2.4118 2.9300 1.3171 1.4471 2.3387 2.4992 1.3597 3.5593 2.3793 1.9301 6.0737 2.3352 5.8637 6.3856 4.9660 8.3810 3.5888 7.1823 4.1630 4.8850 3.3018 6.6199 6.5881 6.5235 6.5897 6.4504 6.2630 6.0219 5.7750 24.3600 23.5266 11.0373 11.4473 3.1774 3.3522 1.4110 1.4259 2.0733 3.0763 6.7068 1.4788 1.5777 1.3467 1.4790 2.3481 1.7878 0.9676 1.4731 1.3762 1.5466 1.8169 0.7911 0.8234 1.3296 1.2690 0.6598 1.5965 1.0301 0.7311 2.2841 0.7312 1.7733 1.8910 1.3476 1.8179 0.6659 1.2202 0.6369 0.6187 0.3384 Unscaled frequency (cm1) Scaled frequency (cm1) Calculated IR intensities Calculated Raman activity Reduced mass (amu) Force constant (mdyne/) Vibrational assignmenta (% TED)

tCH (98) tCH (98) tCH (98) tasCH2 (99) tCH (96) tasCH2 (99) tsCH2 (100) tsCH2 (100) tC@O (82) tC@O (79) tCC (63), bCH (20) tCC (66), bCH (24) bCH (67), tCC (15) bCH (70), tCC (13) rCH2 (97) rCH2 (93) xCH2 (82) tCN (56), bCH2
(29) tCC (60), tCN (31) xCH2 (45), bCH2 (25) bCH (68) tCN (41), xCH2 (37) @CH2 (68), b ring (13) tCC (41), bCH (24), @CH2 (16) bCH (61), tCC (16) tCC (80) @CH2 (56), b ring (22) tCN (40), bCH2 (32), b ring (17) tCC(52), bCH (32) tCC(52), bCH (23) cCH (91) cCH (85) tCC(59), @CH2 (16), cCH (12) bCN (76), bCH2 (14) cCH (92) bC@O (41), bCH (35), @CH2 (22) /CH2 (68), bCH (22) cCH (75), s ring (15) bC@O (51), bCH (27), @CH2 (12) cCH (51), cC@O (26) b ring (68), bCH (11) b ring (57), bCH (13) cC@O (71), cCH (16) b ring (67), tCC (13) cCH2 (68) b ring (52), /CH2 (15), bC@O (11) tCBr (58), b ring (18) s ring (61), cCN (19), bCBr (12) b ring (58), bC@O

T. Karthick et al. / Journal of Molecular Structure 1005 (2011) 202213 Table 7 (continued) Vibrational mode No. Symmetry species Experimental wavenumbers (cm1) FT-IR FTRaman (13) m50 m51 m52 m53 m54 m55 m56 m57 m58 m59 m60
a

211

Unscaled frequency (cm1)

Scaled frequency (cm1)

Calculated IR intensities

Calculated Raman activity

Reduced mass (amu)

Force constant (mdyne/)

Vibrational assignmenta (% TED)

A A A A A A A A A A A

392vw 358s 316w 295w 250w 204w 188w 146w 115w

405 369 325 303 258 212 195 153 120 93 76

396 361 318 297 253 207 191 149 117 91 75

7.4 21.0 2.8 0.6 1.2 3.4 2.6 0.0 3.5 0.9 0.6

2.7 1.7 1.1 1.2 0.5 1.4 0.3 0.9 1.6 4.3 4.4

3.9406 10.4886 2.3719 5.6378 6.9506 6.4072 3.7990 5.0339 8.5112 8.7043 9.7905

0.3653 0.7537 0.1192 0.2068 0.2087 0.1154 0.0538 0.0567 0.0379 0.0065 0.0045

cCN (46), s ring

(18)

cC@O (61), cCH

(18) /CH2 (63), cCN (20) bCBr (51), b ring (30) b ring (51), cCN (20), cCBr (11) Buttery (65) cCBr (62), cC@O (13), s ring (52), bCH (12), cCN (11) s ring (58), cCBr (18), bCN (10) s ring (54), cC@O (13) s ring (56), bCN (17), cC@O (13)

ts, symmetry stretching; tas, asymmetry stretching; b, in-plane bending; c, out-of-plane bending; r, scissoring; x, wagging; @, twisting; /, rocking; s, torsion.

100

80

Transmittance (%)

60

40

20

(a)
0 4000
3000 2000 1500 1000 400

Wavenumber (cm 1)

Transmittance (%)

(b)
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm 1)
Fig. 5. Experimental (a) and calculated (b) FT-IR spectra of N-(2 bromoethyl) phthalimide.

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100

(a)
80

Raman intensity

60

40

20

0 3500

3000

2500

2000

1500

1000

500

100

Wavenumber (cm 1)

(b)
Raman intensity
3500

3000

2500

2000

1500

1000

500

Wavenumber (cm 1)
Fig. 6. Experimental (a) and calculated (b) FT-Raman spectra of N-(2 bromoethyl) phthalimide.

of CABr stretching has been made on the basis of TED. By greater condence, the scaled theoretical wavenumber 497 cm1 (mode no: m47) is assigned to CABr stretching vibrations. The TED contribution to this mode is about 58%. The CABr in-plane (bCBr) and out-of-plane bending (cCBr) vibrations of NBEP molecule coupled with bring and cC@O modes. Hence in the present study, the bands at 295 cm1 and 188 cm1 in FT-Raman are assigned to CABr in-plane and out-of-plane bending vibrations, respectively. The assigned experimental and calculated values of bCBr and cCBr are good agreement with the literature given by Mooney [32]. The buttery mode of NBEP contributes 65% at 204 cm1 in FT-Raman spectra. The calculated value of this mode is excellent agreement with the experimental data.

4. Other molecular parameters In addition to vibrational assignments, hyperpolarizability and HOMOLUMO calculations, several thermodynamic parameters are also calculated at B3LYP/6-311++G(d,p). The calculated thermodynamic properties are presented in the Table 8. The self consistent eld (SCF) energy, zero point vibrational energies (ZPVE), rotational constants and entropy SVib are calculated to the extent of accuracy and the variations in the ZPVEs seem to be insignicant. The total energies and change in total entropy of NBEP at room temperature are only marginal.

5. Conclusion In this work we have performed SCF energy calculations on possible isomers of NBEP. The optimized geometrical parameters, vibrational wavenumbers, non-linear optical properties, HOMO LUMO energy gap of NBEP molecule were predicted at DFT/ B3LYP/6-311++G(d,p) method. All the normal mode frequencies associated with this molecule have been discussed and assigned on the basis of percentage of total energy distribution (TED). Scaled theoretical wavenumbers are compared with experimental FT-IR and FT-Raman wavenumbers. From the hyperpolarizability calculations, we found that the title molecule NBEP has less non-linear optical response. The energy differences between various occupied and unoccupied molecular orbital energies have been computed. The smallest energy gap of 0.18107 a.u is found between HOMO

Table 8 Thermodynamic functions of N-(2 bromoethyl) phthalimide. Parameter Self consistent eld energy Zero point vibrational energy Rotational constants B3LYP/6-311G++(d,p) 3165.4280 a.u 102.08266 (kcal/mol) 1.01396 GHz 0.29530 GHz 0.21476 GHz 112.355 cal/mol K 44.212 cal/mol K 42.485 cal/mol K 32.635 cal/mol K 37.235 cal/mol K

Entropy Specic heat capacity at constant volume Translational energy Rotational energy Vibrational energy

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213

(EHOMO = 0.27966 a.u) and LUMO (ELUMO = 0.09859 a.u). The isodensity surface contour map of frontier orbitals of HOMO and LUMO indicates that there is a charge transfer occurring within the molecule. Molecular electrostatic potential surface map indicates that the most suitable atomic sites for electrophilic attack or for metal coordination are O10 and O18 atoms, while the most probable sites which could be involved in nucleophilic process are ethyl groups. The tting point charges to the electrostatic potential on each atom of the title compound have been computed and are compared with MEP surface. References
[1] V. Krishnakumar, V. Balachandran, T. Chithambarathanu, Spectrochim. Acta A 62 (2005) 918. [2] V. Krishnakumar, M. Sivasubramanian, T. Muthunatesan, J. Raman Spectrosc. 40 (2009) 987. [3] U. Sharma, P. Kumar, N. Kumar, Mini Rev. Med. Chem. 10 (8) (2010) 678. [4] http://www.chemicalland21.com. [5] 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, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austn, 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. AlLaham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian, Inc., Gaussian 03, Revision B.01, Pittsburgh PA, New York, 2003 [6] A.D. Becke, J. Chem. Phys. 98 (1993) 5648. [7] C. Lee, W. Yang, G.R. Parr, Phys. Rev. B 37 (1998) 785. [8] B. Miehlich, A. Savin, H. Stoll, H. Preuss, Chem. Phys. Lett. 157 (1989) 200. [9] T. Sundius, J. Mol. Struct. 218 (1990) 321.

[10] [11] [12] [13] [14] [15] [16] [17] [18] [19]

[20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32]

T. Sundius, Vib. Spectrosc. 29 (2002) 89. Molvib (V.7.0), QCPE Program No. 807 (2002). G. Fogarasi, X. Zhou, P.W. Taylor, P. Pulay, J. Am. Chem. Soc. 114 (1992) 8191. G. Fogarasi, P. Pulay, J.R. Durig, Vib. Spectra Struct. 14 (1985) 125. D.A. Kleinman, Phys. Rev. 126 (1962) 1977. H.T. Varghese, C.Y. Panicker, V.S. Madhavan, S. Mathew, J. Vinsova, C. Van Alsenoy, J. Raman Spectrosc. 40 (9) (2009) 1211. P.L. Anto, Ruby John Anto, H.T. Varghese, C. Yohannan Panicker, D. Philipe, J. Raman Spectrosc. 41 (2010) 113. M. Nsangou, N.E. Jaidane, Z.B. Lakhdar, Internet Electron. J. Mol. Des. 5 (2006) 89. P. Thul, V.P. Gupta, V.J. Ram, P. Tandon, Spectrochim. Acta A 75 (2010) 251. P. Politzer, J.S. Murray, in: D.L. Beveridge, R. Lavery (Eds.), Theoretical Biochemistry and Molecular Biophysics: A Comprehensive Survey, Protein, vol. 2, Adenine Press, Schenectady, New York, 1991. P. Politzer, J. Murray, Theor. Chem. Acc. 108 (2002) 134. Y.X. Sun, Q.L. Hao, Z.X. Yu, W.J. Jiang, L.D. Lu, X. Wang, Spectrochim. Acta A 73 (2009) 892. N. Sundaraganesan, S. Ilakiamani, H. Saleem, P.M. Wojciechowski, D. Michalska, Spectrochem. Acta A 61 (2005) 2995. V. Krishnakumar, R. Mathammal, S. Muthunatesan, Spectrochim. Acta A 70 (2008) 201. N.B. Colthup, L.H. Daly, S.E. Wiberley, Introduction to Infrared and Raman Spectroscopy, third ed., Academic Press, Boston, 1990 (Chapter 13). V. Krishnakumar, Gabor Keresztury, Tom Sundius, S. Seshadri, Spectrochim. Acta A 68 (2007) 845. Jag mohan, Organic Analytical Chemistry, third ed., Narosa Publishing House, 2010. L.J. Bellamy, Infrared Spectra of Complex Molecules, Chapman and Hall, London, 1975. F.R. Dollish, W.G. Fateley, F.F. Bentley, Characteristics Raman Frequencies of Organic Compounds, John Wiley, New York, 1974. p. 170. M. Silverstein, G. Clayton Basseler, C. Morill, Spectrometric Identication of Organic Compounds, Wiley, New York, 1981. G. Socrates, Infrared and Raman Characteristic Group Frequencies, third ed., John Wiley & Sons, Ltd., Chichester, 2001. G. Varsanyi, Assignments for Vibrational Spectra of Seven Hundred Benzene Derivatives, vol. 12, Adam Hilger, England, 1974. E.F. Mooney, Spectrochim. Acta A 20 (1964) 1021.