Vis spectroscopic, NBO analysis of 1-(3-methylthiophen-2-yl)ethanone by ab initio DFT calculations

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Vibrational and UV/Vis spectroscopic, NBO analysis of 1-(3-methylthiophen-2-yl)ethanone by ab initio DFT calculations Ch. Venkat Rao1, D. Rama Sekhara Reddy1,*, D. Jagadeeswara rao2, V. Seeta Ramaiah2, K. Eswar Srikanth1 and Y.Ramakrishna3 1 Department of Chemistry, Krishna University, Machilipatnam, A.P., India-521001 Department of Physics, S.R.K.R Engineering College (A), Bhimavaram, A.P., India-534204 3 Department of Physics, A.U College of engineering (A), Visakhapatnam, A.P., India-530003 2

Abstract The vibrational and electronic properties of 1-(3-methylthiophen-2-yl)ethanone have been studied in the ground state using density functional theory (DFT) employing B3LYP exchange correlation with the 6-31G(d, p) basis set. The theoretically calculated optimized parameters, vibrational frequencies etc., were calculated and presented. The complete assignments of fundamental modes were performed on the basis of the potential energy distribution (PED). UV-Visible spectrum of the compound was predicted theoretically using SAC-CI method and presented. Stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed using natural bond analysis. The first order hyperpolarizability (β) and molecular electrostatic potential of the molecule was computed using DFT calculations. The electron density based local reactivity descriptor were also calculated to explain the chemically reactive site in the molecule. © 2018 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of the Proceedings of National Seminar on Physics and Chemistry of NonCrystalline Materials. Keywords: 1-(3-methylthiophen-2-yl)ethanone (3M2E); DFT; SAC-CI; NBO

1. Introduction Thiophene is one of the most studied heterocycles: it is easy to process, chemically stable, and its synthetic applications have been a constant matter of investigation for the last six or seven decades. The interest in this

* Corresponding author. Tel.: +91-9848591350. E-mail address: [email protected] 2214-7853© 2018 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of the Proceedings of National Seminar on Physics and Chemistry of NonCrystalline Materials.

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heterocycle compound has spread from early dye chemistry [1]. Thiophene derivatives have been reported to possess broad spectrum of biological properties including anti-inflammatory, analgesic, antidepressant, antimicrobial and anticonvulsant activities [2-5]. Vibrational spectroscopy is one of the most widely used methods in spectroscopy and it has been proven to be a powerful technique in the determination of the structural properties of various biologically active compounds. The theoretical studies on vibrational spectra of 1-(3-methylthiophen-2-yl)ethanone and its derivatives have been reported in literature time to time. However, literature survey indicates that there are limited number of investigations on the vibrational spectra of benzofuran and its derivatives. In this study, we report the vibrational, UV studies on 1-(3-methylthiophen-2yl)ethanone using DFT calculations for the first time. 1-(3-methylthiophen-2-yl)ethanone sample in the powder form was purchased from Sigma-Aldrich Chemical Company with a stated purity of 99% and it was used as such without further purification. 2. Computational details As a first step, the most optimized structural parameters, energy and vibrational frequencies of the molecule have been calculated by using B3[6] exchange functional combined with the LYP [7] correlation functional resulting in the B3LYP density functional method at 6-31G(d, p) basis sets. All the computations were performed using Gaussian 09W program [8], Gauss-View molecular visualization program package [9] and Chemcraft molecular visualization program [10] package on an i5 processor. At the optimized structure of the AMT, no imaginary frequencies were obtained, proving that a true minimum on the potential energy surface was found. The optimum geometry was determined by minimizing the energy with respect to all geometrical parameters without imposing molecular symmetry constraints. The NBO calculations [11] were performed using NBO 3.1 program available in the Gaussian 09W package at the DFT/B3LYP level to understand the intra-molecular delocalization or hyper conjugation. UV-Vis spectrum is predicted using TD DFT calculations supplementing with 6-31G(d, p) basis set. 3. Results and discussion 3.1. Molecular geometry The most optimized structural parameters of 3M2E were calculated by DFT /B3LYP level with 6-31 G (d, p) basis set are presented in Table 1. The calculated molecular structure for this compound is found to be non-planar and is as shown in Fig. 1. In order to reveal all possible conformations of AMT, a detailed potential energy surface (PES) scan for C1-C2-C3-S4 dihedral angle was performed.

Fig. 1. Molecular structures of 1-(3-methylthiophen-2-yl)ethanone along with numbering of atom.

The scan was carried out by minimizing the potential energy in all geometrical parameters by changing the torsion angle every 10o for 360o rotation around the bond using 6-31G (d, p) basis set. The shape of the potential energy as a function of the dihedral angle is illustrated in Fig. 2. The total minimum energy obtained by the DFT for the 3M2E was found to be -737.2451 Hartrees. The calculated optimized geometrical parameters are compared with the available experimental data of Ethyl 4-acetyl-5-anilino-3-methyl-thiophene-2-carboxylate [12] as crystal data of 3M2E is not available.

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Fig. 2: Potential energy surface scan for dihedral angle C1-C2-C3-S4 of 1-(3-methylthiophen-2-yl)ethanone. Table 1. Optimized geometrical parameters of 1-(3-methylthiophen-2-yl)ethanone obtained by B3LYP/6-31G (d, p) and B3LYP/6-31G (d, p) density functional calculations Bond lengtha

Value(Ao) 6-31G(d,p)

C1-C2 C2-C3 C3-S4 S4-C5 C5-C1 C2-C6 C3-C7 C7-C9 C7-O8

1.426 1.390 1.753 1.720 1.370 1.508 1.474 1.518 1.226

Exp 1.439 1.365 1.763 1.712 1.409 1.500 1.468 _

1.202

Bond Anglea C1-C2-C3 C2-C3-S4 C3-S4-C5 S4-C5-C1 C5-C1-C2 C1-C2-C6 C3-C2-C6 C2-C3-C7 S4-C3-C7

Value( o ) 6-31G(d,p) Exp 111.50 111.45 91.28 112.21 113.54 121.23 127.26 133.44 115.10

112.44 112.85 91.06 112.47 111.16 121.66 125.89 129.30 117.80

In the table, the atom numbering scheme was given in Fig.1. From the Table 1, it can be seen that there are some deviation in the computed geometric parameters from the experimental value and these differences are due to the crystalline state involves the intermolecular hydrogen bonding, whereas the results of the calculations are applicable to the gas phase. 3.2. Vibrational analysis The maximum number of potentially active observable fundamentals of a non-linear molecule, which contains N atoms, is equal to (3N−6) apart from three translational and three rotational degrees of freedom [13-14]. Hence, AMT molecule has 17 atoms with 45 normal modes of vibrations and considered under C1 point group symmetry. A detailed vibrational description can be given by normal coordinate analysis. The specific assignment to each frequency is attempted through Potential Energy Distribution (PED) method. For this purpose, the full set of defined internal coordinates is given in supplementary material 1. To obtain the normal modes in a molecular coordinate system, local symmetry coordinates for AMT were recommended by Fogarasi and Pulay [15, 16] and were presented in Table 2.

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Table 2: Definition of local-symmetry coordinates and the values of 1-(3-methylthiophen-2-yl)ethanone corresponding scale factors used to correct the B3LYP/6-31G (d, p) (refined) force field.

Symbol a

Definition b

No.(i) Stretching 1 to 2 3-5 6 7-8 9-10 11-12 13-15 16-17 In-Plane bending 18-19 20 21 22-23 24 25

ν(C-H) ν(C-C)ar ν(C-O)sub νCH3ss νCH3ips νCH3ops ν(C-C)sub ν(C-S)

R1, R2. R3, R4, R5 R6 (R7+R8+R9) /√2, (R10+R11+R12) /√2 (2R7-R8-R9)/√6, (2R10-R11-R12)/√6 (R8-R9)/ /√2, (R11-R12)/ /√2 R13, R14, R15. R16, R17.

βC-H βRasy βRsym βC-C βC-O βC-C-C

26-27

βCH3sb

28-29

βCH3ipb

30-31 32-33 34-35

βCH3opb βCH3ipr βCH3opr

(γ18- γ19)/√2, (γ20-γ21)/√2. (a-b)(γ23- γ26) +(a+b) ( γ24- γ25) 22+a(γ23+ γ26)-b (γ24+ γ25) (γ 27-γ28)/√2, (γ 29-γ30)/√2 (γ 31-γ32)/√2 γ 33 (-γ 34- γ 35-γ36+γ 37+ γ38+γ39)/√6, (-γ 40- γ 41-γ42+γ 43+ γ44+γ45)/√6. (-γ 37- γ38-2γ39)/√6, (-γ 43- γ44-2γ45)/√6. (γ 38- γ39)/√2, (γ 44- γ45)/√2 (2γ 34- γ 35-γ36)/√6, (2γ 40- γ 41-γ42)/√6 (γ 35-γ36)/√2, (γ 41-γ42)/√2

ωC-H ωC-O ωC-C

ρ 46, ρ47 ρ 48 ρ 49 ρ 50

τRasy τRsym τOCCC τSCCO τSCCC

b(τ51+τ55)+a(τ52+τ54)+ τ53 (a-b)( τ54- τ52)+(1-a) (τ55- τ51) τ 56 τ 57 τ 58

Out of plane bending 36-37 38 39-40 Torsions 41 42 43 44 45

The Raman activity (Si) calculated by Gaussian 09W and adjusted during scaling procedure with MOLVIB were converted to relative Raman intensity (Ii) using the following relation from the basic theory of Raman scattering [17, 18] f ( o - i )4 S i Ii   i [1- exp (-hc i / KT )] (1) Here νo is the exciting frequency (in cm-1 units); νi is the vibrational wavenumber of the normal mode; h, c, k are the universal constants and f is suitably chosen common normalization factor for all the intensities. For the plots of simulated IR and Raman spectra, pure Lorentzian band shapes were used with a bandwidth (FWHM) of 10 cm-1. The theoretically simulated spectra are more regular than the experimental ones, because many vibrations presenting in condensed phase leads to strong perturbation of infrared intensities of many other modes.

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Fig. 3 & Fig. 4: Theoretical IR and Raman spectra of 1-(3-methylthiophen-2-yl)ethanone

The simulated IR and Raman spectra for AMT are shown in Fig.3 and Fig.4 respectively. The RMS error of the observed and calculated frequencies (un-scaled) of was found to be 49.6 cm-1 (Table 3). Therefore, we provide the following tentative assignments for almost all intense spectral features in the vibrational spectra of the molecule. 3.3. Vibrational frequency Vibrational frequencies were calculated by B3LYP/6-31G (d,p) method. 3.3.1 C-H Vibrations The existence of one more aromatic rings in a molecule is normally determined from the C-H and C-C = C ring related vibrations. The C-H stretching occurs above 3000 cm-1 and is typically exhibited as a multiplicity of weak to moderate bands (Hunt et al. 1987). In the present theoretical study, the FTIR band in the region 3300-3100 cm-1 are assigned to aryl C-H stretching vibrations. The C-H in plane bending vibration usually occurs in the region 1400-900 cm-1 and very useful for characterization purpose (Castillo et al. 2012). For AMT, the calculated frequencies were 1323, 1314, 1275, 1241, 1217, 1179, 1119, 1057, 1030 cm-1. The C-H out of plane deformations is observed between 1000-500 cm-1 for the title compounds. 3.3.2 C-S Vibrations In our present study, the C-S stretching vibrations are observed at 867 cm-1. 3.3.3 C = C Stretching The ring carbon – carbon stretching vibrations occur in the region 1650-1400 cm-1. The c=c stretching is observed at 1645, 1573, 1535 cm-1. 4. NBO analysis NBO analysis provides the most accurate possible ‘natural Lewis structure’ picture of ø, because all orbital details are 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 filled and virtual orbital spaces that could enhance the analysis of intra- and intermolecular interactions. It also provides a convenient basis for investigating charge transfer or conjugative interaction in molecular systems. The second order Fock matrix was carried out to

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evaluate the donor–acceptor interactions in the NBO analysis [19]. Some electron donor orbital, acceptor orbital and the interacting stabilization energy resulting from the second-order micro disturbance theory is reported [20, 21]. The result of interaction is a loss of occupancy from the concentration of electron 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 2 Fij2 σ|F|σ E(2)= - n σ * = - nσ ε σ -εσ ΔE (2) 2 2 Where, σ|F|σ or F ij is the Fock matrix element i and j NBO orbitals, εσ* and εσ are the energies of σ and σ* NBOs and nσ is the population of the donor σ orbital. The larger is the E(2) value, the more intensive is the interaction between electron donors and electron acceptors, i.e. the more donating tendency from electron donors to electron acceptors and the greater the extent of conjugation of the whole system. Delocalization of electron density between occupied Lewis type (bond or lone pair) NBO orbitals and formally unoccupied (antibonding and Rydberg) nonLewis NBO orbitals correspond to a stabilizing donor–acceptor interaction. The NBO analysis has been performed on the compound using NBO 3.1 program as implemented in the Gaussian 09W package at the DFT-B3LYP/631G(d,p) level of theory in order to elucidate the intramolecular interaction, re-hybridization and delocalization of electron density within the molecule, which are presented in Table 3. Τable 3. Second order perturbation theory analysis of fock matrix in NBO basis for 1-(3-methylthiophen-2-yl) ethanone Donor(i)

Type

Ed/e

Acceptor(j)

Type

Ed/e

E(2)

E(i)-E(j)

f(i,j)

C1-C2

σ

1.97382

C3-C7

σ*

0.06385

4.82

1.13

0.066

C5-H11

σ*

0.01280

1.99

1.21

0.044

C1-C5

π

1.82891

C2-C3

π*

0.37177

17.23

0.30

0.067

C2-C3

π

1.78300

C1-C5

π*

0.31337

14.25

0.28

0.058

C7-O8

π*

0.17439

22.71

0.29

0.073

C3-S4

σ

1.97295

C2-C6

σ*

0.01850

5.27

1.08

0.068

C3-C7

σ

1.98430

C2-C3

σ*

0.02896

4.52

1.26

0.068

S4-C5

σ

1.98140

C1-H10

σ*

0.01531

4.01

1.15

0.061

C6-H12

σ

1.98858

C2-C3

σ*

0.02896

5.04

1.08

0.066

C7-O8

π

1.99575

C2-C3

π*

0.37177

5.24

0.38

0.044

C9-H15

σ

1.97562

C7-O8

π*

0.17439

3.99

0.53

0.043

C9-H17

σ

1.97406

C7-O8

π*

0.17439

4.80

0.53

0.047

S4

LP

1.99932

C1-C5

π*

0.01480

26.26

0.25

0.075

C2-C3

π*

0.37177

21.47

0.26

0.068

The intramolecular hyper conjugative interactions are formed by the orbital overlap between σ(C–C) → σ*(C–C), π(C–C) → π*(C–C) which results in ICT (Intra molecular charge transfer) causing stabilization of the system. These interactions are observed as increase in electron density (ED) in C–C antibonding orbital that weakens the respective bonds. The most important interactions in the heterocyclic Thiophene molecule having lone pair S4 (1) with that of antibonding C1-C5 and C2–C3, results the stabilization of 26.26 and 27.07 kJ/mol. respectively. The interaction between the C2-C3,C1-C5 with antibonding of C6-H13 and C5–H11 resulting stabilization energy 1.57 and 1.99 kJ/mol which denotes very small delocalization. The interaction between lone pair C2-C3 (2) with antibonding C1C5 and C7-O8 resulting stabilization energy 14.25 and 22.71 kJ/mol which denotes larger delocalization. 5. HOMO, LUMO energy gap The conjugated molecules are characterized by a small highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) separation, which is the result of a significant degree of intra-molecular charge transfer (ICT) from the end-capping electron-donor groups to the efficient electron-acceptor groups through πconjugated path. The strong charge transfer interaction through π-conjugated bridge results in substantial ground

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state donor–acceptor mixing and the appearance of a charge transfer band in the electronic absorption spectrum. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are the main orbitals take part in chemical stability [22].

Fig. 5. The atomic orbital components of the frontier molecular orbital (HOMO—MO: 37, LUMO—MO: 38) of 1-(3-methylthiophen-2yl)ethanone. Table 4: The calculated quantum chemical parameters for 1-(3-methylthiophen-2-yl)ethanone obtained by B3LYP/6-31 G(d,p) calculations. Property Total energy (eV)

1-(3-methylthiophen-2-yl)ethanone -20193.71

EHOMO (eV)

-6.62434

ELUMO (eV)

-1.58234

EHOMO-ELUMO (eV)

-5.04210

Electronegativity (χ)eV

4.10334

Chemical hardness(η)eV

-2.52102

Electrofilicity index (ω) eV

-3.33940

Global Softness (σ)eV

0.39666

Total energy change(ΔET) eV

0.63025

Dipole moment(D)

4.1021

The HOMO represents the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain an electron. The HOMO and LUMO energy and some other parameters calculated by B3LYP/6-31G(d, p) method are given in Table 4. The HOMO is located over the Thiophene ring and methyl group as well. The LUMO is located over whole molecule except H10, H12, H16 parts. The other molecular orbitals of 3M2E under Cs symmetry are presented in Fig. 6. The HOMO and LUMO gap has been calculated to be 3.12386 eV and its equivalent wavelength is 799.02 nm. Hence this molecule can be used as a potential source for UV light. The HOMO and LUMO energy gap explains the eventual charge transfer interactions taking place within the molecule. Moreover, these orbital significantly overlap in their position for the compound. The frontier orbital gap helps characterize the chemical reactivity and kinetic stability of the molecule. A molecule with a small frontier orbital gap is more polarizable and is generally associated with a high chemical reactivity, low kinetic stability and is also termed as soft molecule. The dipole moment in a molecule is another important electronic property that results from non-uniform distribution of charges on the various atoms in a molecule. It is mainly used to study the intermolecular interactions involving the Van der Waal type dipole–dipole forces, etc., because larger the dipole moment, stronger will be the intermolecular interactions. The calculated dipole moment value for the molecule is 4.1021 Debye (Table 4) which indicates that the compound exhibits more molecular interactions. Ultraviolet spectra analyses of AMT have been investigated by TD-DFT/B3LYP/6-31G (d, p) method. The calculated visible absorption maxima of λmax which are a function of the electron availability have

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been reported in Table 5. 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. Table 5. The UV–Vis excitation energy and oscillator strength for 1-(3-methylthiophen-2-yl)ethanone calculated by TD-DFT/B3LYP/6-31G(d,p) method. No. 1

Energy (cm-1) 29657.21

Wavelength (nm) 337.1861

Osc. Strength 0.0001

Symmetry Singlet-A

Major contribs H-1->LUMO (87%) H-1->L+1 (2%), HOMO->LUMO (8%)

2

38167.23

262.0049

0.0923

Singlet-A

H-2->LUMO (80%), HOMO->LUMO (16%)

3

39469.82

253.3581

0.2031

Singlet-A

H-2->LUMO (14%), HOMO->LUMO (73%)

4

50070.44

199.7186

0.0011

Singlet-A

H-1->L+1 (79%) H-1->LUMO (3%), H-1->L+3 (5%), HOMO->L+1 (8%)

5

52035.22

192.1775

0.0004

Singlet-A

HOMO->L+2 (87%) H-1->L+2 (5%), HOMO->L+1 (7%)

Fig. 6. Theoretical UV/Vis spectra of 1-(3-methylthiophen-2-yl)ethanone

As can be seen from the UV-Vis spectra absorption maxima values have been found to be 285 and 185 nm. The λmax is a function of substitution, the stronger the donor character of the substitution, the more electrons pushed into the molecule, the larger λmax. These values may be slightly shifted by solvent effects. The role of subsistent and solvent may influence the UV-Vis spectrum. Owing to the interaction between HOMO and LUMO orbital of a structure, transition state transition of π-π* type is observed with regard to the molecular orbital theory. 6. NLO Properties The second-order polarizability or first hyperpolarizability β, dipole moment µ and polarizability α was calculated using HF/6-31G (d, p) basis set on the basis of the finite-field approach. The complete equations for calculating the magnitude of total static dipole moment μ, the mean polarizability α0, the anisotropy of the polarizability Δα and the mean first hyperpolarizability β0, using the x, y, z components from Gaussian 09W output is as follows

   

o



  2



1/2

  (

2 x xx

   

2 y

   

yy

2

(3)

z

zz

(4)

3

[( xx   yy )  ( yy   xx )  6 2

2 x

 

2 y

 

2

2 z

)1/ 2

2

1/2

xx

]

(5) (6)

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and



x



y



z

   

xxx

yyy

 

 

 

xyy

  xxy  

zzz

 

xxz

xzz

(7) (8)

yyz

(9)

yzz

 

Since the values of the polarizabilities (α) and hyperpolarizability (β) of Gaussian 09W output are reported in atomic units (a.u), the calculated values have been converted into electrostatic units (esu) (α: 1a.u= 0.1482 x 10-12 esu, β: 1 a.u = 8.6393×10-33 esu). The total first hyperpolarizability the title compound has been calculated to be 5.425X10-30 esu as shown in Table 6. Table 6. Calculated all β components and β tot value of 1-(3-methylthiophen-2-yl)ethanone by HF/6-31G (d, p) method 1-(3-methylthiophen-2-yl)ethanone βxxx

-27.3754991

βxxy

-0.4150627

βxyy

-20.2936261

Βyyy

-6.11334452

βxxz

-37.9329759

βxyz

-2.4512329

Βyyz

20.0804184

βxzz

55.5723915

βyzz

0.8544085

βzzz

232.7942982

β total (esu)

5.425 ×10-30 esu

This result shows that the compound is one of the best materials for NLO applications. 7. Molecular electrostatic potential maps The molecular electrostatic potential (MESP) is widely used as a reactivity map displaying most probable regions for the electrophilic attack of charged point-like reagents on organic molecules[28, 29]. The molecular electrostatic potential (MESP) V(r) at a point r due to a molecular system with nuclear charges {ZA} located at {RA} and the electron density ρ(r) is given by (10) V(r) = ΣN A [(ZA / |r-RA|) - ∫ρ(r’)d3r’/|r-r’| Where, N denotes the total number of nuclei in the molecule and the two terms refer to the bare nuclear potential and the electronic contributions, respectively.

Fig. 7. B3LYP/6-31G (d, p) calculated 3D molecular electrostatic potential maps of 1-(3-methylthiophen-2-yl)ethanone.

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8. Conclusions In the present study, the detailed investigations on 1-(3-methylthiophen-2-yl)ethanone (3M2E) were performed using quantum chemical calculations. The structural, electronic, UV-Vis analysis, and vibrational frequencies of the title compound have been calculated by the DFT/B3LYP/6-31G(d,p) methods. The optimized geometric parameters (bond lengths and bond angles) of 3M2E are theoretically determined. On the basis of calculated results, assignments of fundamental vibrational modes of the title compound were examined based on the results of the PED output obtained from normal coordinate analysis. The nonlinear optical property of the studied compound was investigated by determining the ground-state dipole moment, the mean polarizability, the anisotropy of the polarizability, and the mean first-order hyperpolarizability using the DFT/B3LYP method. Finally, it is concluded that the investigated compound can be used as an NLO material. Moreover, in order to obtain information about the negative and positive regions that are possible sites for the electrophilic and nucleophilic attack, respectively, the 3D molecular surfaces were simulated. Acknowledgements The authors express their thanks to Krishna University, Machilipatnam and S.R.K.R Engineering College (A), Bhimavaram for providing lab facility. References [1] W.J. King, F.F. Nord, J.org.Chem.1949, 14, 638 [2] K.I. Molvi, K.K. Vasu , S.G. Yerande, V.Sudarsanam, N. Haque, Eur.J.Med.Chem [3] N.Satheesha Rai, B.Kalluraya, B. Lingappa, S.Shenoy, V.G. Puranic, Eur.J.Med.Chem. 43 (2008) 1715-1720 [4] B.V.Asthalatha, B. Narayana, K.K. Vijaya Raj, N.Suchetha Kumari, Eur.J.Med Chem. 42 (2007) 719-728 [5] K.K. Park, H. Seo, J.–G. Kim, I.-H. Suh, Tetrahedron Lett. 41 (2000) 1393 [6] A.D. Becke, Phys. Rev. A 38 (1988) 3098 [7] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785 [8] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, 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, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian 09W, Revision D.01, Gaussian, Inc.,Wallingford CT, 2009. [9] A. Frisch, A. B. Nielsen, A. J. Holder, Gaussview User’s Manual Gaussian Inc., Pittsburg. [10] www.chemcraft.org. [11] E.D. Glendering, A.E. Reed, J.E. Carpenter, F. Weinhold, NBO version 3.1, TCI, University of Wisconsin, Madison, 1998. [12] Yahia Nasser Mabkhot, Fatima, Assem Barakat, M. Iqbal Choudhary, An Sammer Yousuff Acta Crystallographica Section E (2013) 16005368 [13] M. Silverstein, G. Clayton Bassler, C. Morril, Spectroscopic Identification of Organic Compounds, John Wiley, New York, 1981. [14] E.B. Wilson, J.C. Decius, P.C. Cross, Molecular Vibrations, Dover Publ. Inc., New York, 1980. [15] P. Pulay, G. Fogarasi, F. Pang, and J. E. Boggs , J. Am. Chem. Soc. 101 (1979) 2550 [16] G. Fogarasi, X. Zhou, P.W. Taylor, P. Pulay, J. Am. Chem. Soc. 114 (1992) 8191 [17] P.L. Polavarapu, J. Phys. Chem. 94 (1990) 8106 [18] G. Keresztury, S. Holly, J. Varga, G. Besenyei, A.Y. Wang, J.R. Durig, Spectrochim. Acta A. 49 (1993) 2007 [19] M. Sarafran, A. Komasa, E.B. Adamska, J. Mol. Struct. (Theochem.) 827 (2007)101-. [20] C. James, A. AmalRaj, R. Reghunathan, I. Hubert Joe, V.S. JayaKumar, J. Raman Spectrosc. 37 (2006) 1381 [21] L.J. Na, C.Z. Rang, Y.S. Fang, J. Zhejiang Univ. Sci. 6B (2005) 584 [22] Akhil R. Krishnan, H. Saleem, S. Subashchandrabose, N. Sundaraganesan, S. Sebastain, spectrochimica Acta Part A 78 (2011) 582 [23] S.K. Ignatov, Moltran v.2.5 - Program for molecular visualization and thermodynamic calculations, University of Nizhny Novgorod, 2004.