Journal of Computational Chemistry & Molecular Modeling

ISSN: 2473-6260

Impact Factor: 0.562

VOLUME: 3 ISSUE: 2

Page No: 294-312

Investigation on Spectral properties of 3-Chloro-3'-Methoxystilbene for Anticancer Drugs Application: Using Density Functional Theory


Affiliation

Ragavana, A. Prakasamb

aDepartment of Physics, Periyar University, Salem - 636 011, India.

bDepartment of Physics, Thiruvalluvar Government arts college, Rasipuram, Namakkal – 637 401, India

Citation

I. Ragavan, A. Prakasam, T.Saravana Kumaran, Investigation on Spectral properties of 3-Chloro-3'-Methoxystilbene for Anticancer Drugs Application: Using Density Functional Theory(2019)Journal of Computational Chemistry & Molecular Modeling 3(2)p:294-312

Abstract

The ground state optimized structure and spectroscopic analysis of 3-chloro-3'-methoxystilbene (3C3'MS) were studied experimentally by FT-IR techniques and computationally by the first principle density functional theory (DFT) and Hartree-Fock (HF) method with 6-311++G (d, p) level of theory. The computational vibrational frequencies have been assigned and they agreed satisfactorily with experimental FT-IR and FT-Raman spectra. The computed maximum wavelength of absorption of 3C3'MS are calculated in different solvents (Acetonitrile, Methanol and Ethanol) by TD-DFT method. The experimental available 1H and 13C nuclear magnetic resonance chemical shifts calculations have been calculated by using the Gauge independent atomic orbital (GIAO) method and compared with the computational studies. The NBO atomic charges analysis in conjunction with spectral data recognized the occurrence of intra-molecular interactions such as hyperconjugative, mesomeric and steric effects in 3C3'MS. Electronic distribution and Frontier molecular orbital energy values of 3C3'MS are discussed in terms of intra-molecular interactions. Computed values of Mulliken charges, Quantum Chemical descriptors and thermodynamic properties of 3C3'MS along with molecular electrostatic potential (MEP) are reported. Moreover, the estimation of the molecule confirms the biological behavior.

Keywords: FT-IR, FT-Raman, NMR spectra, NBO, NLO and NPA analysis, Thermodynamic properties, MEP analysis.

Introduction

Stilbene and its derivatives are one of the most thoroughly studied compounds from the standpoint of mechanistic and preparative photochemistry [1-5]. The importance of the ring closure reaction channel in cis and trans-stilbene was recognized early [6] and most in recent time’s stilbene has become a prototype for ultrafast studies of photoisomerization [7-10]. The importance of stilbene photochemical analogous studies has been performed for only a limited range of stilbene and its derivatives. Our final goal is to obtain a clearer picture of the effect of different solvents and substituents on photochemical processes for cis and trans-stilbene derivatives. In these derivatives are important oligomeric compounds with a broad range of biological action, including hormonal, hypocholsterolemic, Sympathomimetic, antifungal, antiallergic, Human hemoglobin, antibacterial, antimalarial, Human serum albumin and anticancer activity. 3-chloro-3'-methoxystilbene are very important bioactive molecule [11-14]. The most famous stilbene derivatives, which was used medically for prostate and breast cancer, and to prevent threatened abortions [15-18]. Seigo sanoh et al. reported the trans-stilbene is metabolically activated to estrogenic compounds by liver microsomal enzyme molecular system. The physical requirement for estrogenic activity of different stilbene derivatives (Cis and Trans) including proestrogens [19]. Kyosuke Tsumura et al. reported DFT and TD-DFT, together with the analytical calculation of numerical and gradients calculation of the Hessian matrix has been applied to calculate the FT-IR, FT-Raman and fluorescence excitation spectrum of trans-stilbene (tSB) in the lowest excited singlet (S1) state [20]. The Excited-state reduction of cis-stilbene and trans-stilbene is outlined with femtosecond computed FT-Raman spectroscopy, using Sn→S1 resonance conditions. For isomers, decay in FT-Raman shift, intensity of spectral positions and mind broadening of the bands specify IVR. In n-hexane this process effectively takes 0.5-0.7 ps [21]. Rajat K. Chaudhuri et al. reported Molecular  geometries are calculated for the ground state and excited states of 4a,4b-dihydrophenanthrene (DHP), cis-stilbene, and trans-stilbene from calculations accomplished with the developed fundamental orbital, complete active space configuration intermolecular interaction (IVO-CASCI) method. The calculations indicate that a nonplanar conformer of tSB is the most stable between the photoisomers [22].The photoisomerization dynamics of tSB have been well studied in the lowest excited state, but much less is known about the performance following excitation to higher excited states. This contribution reports a combined study of the spectroscopy and dynamics of two-photon available states above S1. Two-photon absorption (2PA) measurements using a broadband pump−probe technique reveal distinct bands near 5.1 and 6.4 eV are reported by Amanda L. Houk et al [23].

Nowadays, Modern vibrational spectroscopy has become a very popular analytical technique for solving many chemical problems. This is especially true of studies using Raman spectroscopy is a powerful technique, which gives information about the vibrations modes of the atoms and molecular structure, specific information on various chemical composition and Fourier transform infrared spectroscopy (FT-IR) is as an analytical method to identification of the functional groups, the degree of conjugation and interaction with drugs. The problem of signal vibrations however, as well as understanding the relationship between the observed vibration spectra and molecule structure, and chemical reactivity can be difficult. Even identification of important vibrational modes often generates controversy [24].  Recently, computational technique and DFT is an advance quantum chemical approach that plays an important role in the understanding of molecular system, vibrational spectrum and of the various properties of biological activity [25-28]. In particular for polyatomic molecules the quantum chemical method lead to the calculation of the  more perfect molecular system and vibrational Spectrum (Infrared and Raman spectroscopies) than the conventional ab initio RHF and MP2 method [24] and the three-parameter B3LYP density functional, which includes Becke’s gradient exchange correction [29] and the Lee-Yang-Parr correlation functional [30].

In previous work, we wish to report the experimental and theoretical investigation of vibrational spectral analysis and ground state geometric structure of this bioactive 3-Chloro-3'-Methoxystilbene molecule and their results have been discussed. Moreover, the calculated vibrational wavenumber of potential energy distribution (PED) was assigned and Molecular Electrostatic Potential (MEP) map of title compound has been reported. The HOMO-LUMO energy gap to supports to pharmacological active property and Natural bond orbital (NBO) charge analysis has been performed to investigate charge transfer interactions and the hydrogen bonding within the molecule. The electronegativity, chemical hardness and softness values were also considered by utilizing frontier molecular orbital energy gaps of title compound.

Materials & Methods

2.1. Experimental Details

This chemical with a purity of 99% is purchased form Alfa Aesar chemical suppliers (India) and were used as received. FT-IR measurements were performed using Mattson 1000 FT-IR spectrometer in the 4000 and 400 cm-1 region. The FT-Raman spectrum of 3C3'MS  was recorded between the region 4000 and 50 cm-1 using a Bruker FRA 106/S FT-Raman instrument using 1064 nm excitation from an Nd: YAG laser. The detector used was a liquid nitrogen cooled Ge detector. 1H NMR and 13C NMR spectrum was recorded at 400 MHZ on BRUKER AV-III 400 MHZ instruments.

2.2. Computational details

The theoretical calculations were performed using the Gaussian 09 program package [31]. The optimized geometries were obtained employing DFT and HF [32, 33] functional in conjunction with 6-311++G (d, p) basis set. Subsequently, the vibrational IR and Raman spectra were calculated at harmonic approximation. All the calculated computed harmonic frequencies were real, which confirm that the optimized structures correspond to minimum energies. The internal coordinates of the molecule were converted to the local symmetry coordinates. The distributions of assignment of the computed wavenumbers have been aided by means of MOLVIB-7.0 program [34, 35]. The Cartesian representation of the force constants were transferred to a non-redundant set of symmetry coordinates, internal coordinate system recommended by Pulay et al. [36] is used for the assignment of vibrational modes. All the molecular structures are pictured using software Gauss-view [37]. 1H and 13C NMR isotropic shielding were calculated by GIAO method using optimized parameters obtained from DFT/6-311++G (d, p) method. The electronic properties such as oscillator strengths of electronic singlet-singlet transitions, absorption wavelengths and calculate energies were determined by TD-DFT method and Hence, the HOMO and LUMO energies and chemical hardness, softness, electrophilicity index and electronegativity were assumed from electron affinity and ionization potential have also been evaluated in the present study.

Results

4.1 Molecular Geometry

The most optimized geometrical parameters such as, bond lengths, bond angles and dihedral angles of title compound calculated at initio DFT and HF methods with 6-311++G(d,p) level of theory and optimized structure of the host molecule along with numbering scheme in Fig. 1. The calculated bond lengths between C12-C2, C5-Cl17 in DFT and HF methods are found to be 1.3514, 1.3315 Å and 1.8309, 1.8117 Å respectively. The bond angle between C5-C4-20 in HF and DFT are 120.0677 and 119.6667o respectively in Fig. 2b.The dihedral angle between C8-C3-C4-H20 in HF and DFT are 180.001o and 179.9987o respectively. The Computed geometrical parameters can be used to determine the other parameters of 3C3'MS. The bond lengths, bond angles and dihedral angles were referred from [38]. Fig.2. Graphical representation of correlation coefficient and linear relationships of between the DFT and HF bond lengths, bond lengths and dihedral angles were determined for 6-311++G(d,p) basis set.

The optimized bond lengths of C-H in methyl ring in calculated range from 1.0893, 1.0965, 1.0965 Å and 1.0762, 1.0823, 1.0823 Å for 3C3'MS. The C-H bond angles are found 109.7164, 109.6621, 109.7152 and 109.6616, 109.5451, 109.7381 Å for 3C3'MS respectively, from DFT and HF/6-311++G (d, p) methods, which are in good agreement with calculated values for C-H bond lengths and bond angles of methyl ring.

https://www.siftdesk.org/articles/images/558/1.png

Fig. 1   Optimized geometrical structure

https://www.siftdesk.org/articles/images/558/2.png

Fig. 2   Bond lengths, bond angles and dihedral angles differences between DFT and HF approaches

4.2 HOMO-LUMO energy gap

Frontier molecular orbitals (FMOs) play a major role in the kinetic stability or molecular chemical reactivity and the interactions between atoms. They are measured to be effective in determining the characteristics of the molecule such as pharmaceutical and biological activities. The organic molecule containing conjugated π electrons characterized by a small HOMO-LUMO separation energy, which is the result of a significant degree of Intramolecular change transfer (ICT) from the end-capping electron donor groups to the efficient electron acceptor groups through conjugated path [39]. The calculated HOMO-LUMO energy gap of the title molecule is -4.17 eV at the B3LYP level, respectively. The Large energy gap is basically a significance of the large stabilization of the LUMO due to the strong electron−accepting ability of the electron−acceptor group. The graphical diagram of HOMO and LUMO orbitals and their respective positive and negative regions are shown in Fig. 3. Such a plot suggests that in the HOMO → LUMO excitation the benzene ring π electrons are transferred to chloride group. The chemical reactivity of organic molecules such as chemical hardness and softness can be calculated from HOMO and LUMO energy gap values. The atomic π-orbital’s point towards each other and an increase in π-character points the fact that σ-bonds are stronger as showed by natural bond analysis. A highly delocalized LUMO indicates that the electrons can more readily move around the molecule from HOMO-LUMO and hence an improved ICT [40] shown in Table 1. The HOMO electrons are mostly localized on the methyl group attached to the benzene ring while LUMO is mainly delocalized on the benzene ring indicating the presence of favorable atomic center within 3C3'MS for possible nucleophile attacks(hydrogen bond acceptor)  revealing its bioactivity. Both the HOMO and LUMO are mainly localized around the two benzene rings which show that they are π type orbitals. There are lots of applications available for the use of HOMO and LUMO energy gap as a computational calculation.

https://www.siftdesk.org/articles/images/558/3.png

Fig. 3 Schematic view of the important Molecular Orbitals of TD-DFT/6-311++G (d, p) method.

 

Table 1. Molecular Properties end energy gap (eV) between molecular orbitals involved in electronic transitions of 3C3'MS.

Global Activity

DFT

Acetonitrile

Ethanol

HOMO (eV)

5.77

5.93

5.97

LUMO (eV)

1.6

1.74

1.51

Energy gap(eV)

4.17

4.19

4.46

Hardness (ƞ)

2.08

2.09

2.23

softness (S)

0.240

0.239

0.224

Ionization potential (µ)

-3.68

-3.83

-3.74

Electronegativity (χ)

3.68

3.83

3.74

Electrophilicity index (ω)

3.233

3.509

3.136

 

Table 2. Definition of internal coordinates of 3C3'MS.

No (i)

 

Symbol

Type

 

Definition

Stretching

1-15

 

C-C

C1-C2, C2-C3, C3-C4, C4-C5, C5-C6, C6-C7, C7-C8, C8-C3, C1-C9, C9-C10, C10-C11, C11-C12, C13-C14, C14-C9

16-25

 

C-H (Ring)

C1-H18, C2-H19, C4-H20, C6-H21, C7-H22, C8-H23, C10-H24, C12-H25, C13-H26, C14-H27

26-28

 

C-H(methyl)

C16-H28, C16-H29, C16-H30

29

 

C-CI

C5-CI17

30-31

 

C-O

C11-O15,C16-O15

Bending

32-43

 

C-C(Ring)

C3-C4-C5, C4-C5-C6, C6-C7-C8, C7-C8-C3, C8-C3-C4, C9-C10-C11, C10-C11-C12, C11-C12-C13, C12-C13-C14, C13-C14-C9, C14-C9-C10

44-46

 

C-C-C

C9-C1-C2, C1-C2-C3, C2-C3-C4

47-48

 

C-C-C

CI17-C5-C4, CI17-C5-C6

49-51

 

H-C-H

H28-C16-H29, H29-C16-H30, H30-C16-H29

52-54

 

O-C-H methyl

O15-C16-H28, O15-C16-H29, O15-C16-H30

55-65

 

C-C-H

C3-C4-H20, C5-C6-H21, C6-C7-H22, C7-C8-H23, C2-C3-H19, C2-C1-H18, C9-C14-H27, C13-C14-H26, C13-C12-H25, C11-C10-H24, C9-C1-H18

66

 

C-O-C

C11-O15-C16

67-68

 

C-C-O

C12-C11-O15, C10-C11-O15

Out-of-plane bending

69-76

ωi

C-H(Ring)

H20-C4-C5-C6, H21-C5-C6-C7, H22-C6-C7-C8, H23-C7-C8-C3, H24-C9-C10-C11, H25-C11-C12-C13, H26-C12-C13-C14, H27-C9-C14-C13

77

ωi

C-O

C12-C11-O15-C16

Torsion

78-81

τi

τ C-C Ring

C3-C4-C5-C6, C4-C5-C6-C7, C5-C6-C7-C8, C6-C7-C8-C3

82-84

τi

τ C-CH3

(C12)C11-C15-C16-H28, (C12)C11-C115-C16-H, (C12)C11-C15-C16-H30

85

τi

τ CI-C

CI-C4-C5-C6

86-87

τi

τ C-H

H20-C4-C5-CI17, H21-C6-C5-CI17

 

4.3 Vibrational analysis

The vibrational spectral analysis is to end vibrational frequencies connected with specific molecular structures of calculated title molecule. The normal vibrations are distributed as 56A'+31A'' considering Cs symmetry. All the 87 normal modes of vibrations are active in both IR and Raman. Vibrational wavenumber was calculated using the DFT and HF methods with the single split valence basis set 6-311++G (d, p). Table 3 the vibrational assignments in the present study are based on the scaled wavenumbers DFT and HF/6-311++G (d, p) vibrational frequencies, Reduced Mass, Raman activity, IR intensities, Depolarization Ratio, Force Constants and fundamental modes descriptions (characterized by PED) of the title compound. The comparison between the observed frequencies and the computational FT-IR and Raman spectra support each other. Including of electron correlation in computational theory to a certain extend makes the frequency values smaller in comparison with the HF frequency data. All frequency modes are active both in IR and Raman Spectra. For this purpose, the full set of 87 normal internal coordinates and description of vibrational assignments of fundamental modes can be given by means of normal coordinates have been reported in Table 2. The calculated and experimental of FT-IR [41], FT-Raman spectra are shown in Figs. 4 and 5.

https://www.siftdesk.org/articles/images/558/4.png

Fig. 4 Experimental and theoretical FT-IR spectra.

https://www.siftdesk.org/articles/images/558/5.png

Fig. 5 Experimental and theoretical FT-Raman spectra.

 

Table 3. Experimental Theoretical harmonic frequencies (cm-1) of the 3C3'MS molecule along with the assignments of vibrational modes basing on PED results.

 

 

S.no

 

Experimental

Wavenumber (cm-1)

 

Scaled

Wavenumber (cm-1)

IR Intensty

(Ai)

Raman
active
(Ii)

Depolarisation Ratio

Reduced Mass (µ)

Force

Constants (K)

Assignments with PED (%)

FT-IR

FT-Raman

DFT

HF

dIR-Ra

 

-

-

3295

3247

48

3.8458

172.844

0.7472

1.092

6.8043

νCH(99)

1

3182

3179

3290

3241

49

14.805

158.127

0.75

1.0924

6.7681

βipd CH3(98)

2

3153

 

3278

3228

50

1.395

106.788

0.75

1.0906

6.7088

βipd CCC(391)

3

3089

3160

3276

3226

50

16.675

12.2342

0.2055

1.092

6.6998

δCH3(91)

4

3060

3053

3275

3225

51

9.6079

71.0921

0.1788

1.0924

6.6952

τRCCCC(90)

5

-

3011

3270

3221

49

7.7395

24.6103

0.3838

1.0906

6.6696

νCH(32), ν1CH(89)

6

3015

-

3252

3205

47

8.9023

73.4806

0.3243

1.0872

6.5837

τCOCC(87)

7

3001

2996

3245

3199

46

9.094

71.0542

0.4637

1.0873

6.5567

βipd CH3(86)

8

-

2989

3222

3181

41

22.978

150.064

0.4767

1.0987

6.5505

νCH(86)

9

-

 

3215

3176

39

38.311

2.7141

0.4785

1.0855

6.4538

νCH(86)

10

-

-

3214

3166

48

1.6292

39.3106

0.4782

1.0904

6.4432

ν OC(81)

11

2995

2816

3142

3103

39

44.149

70.5652

0.5042

1.1045

6.2681

νCH(70)

12

2985

2791

3078

3032

46

56.836

163.546

0.2039

1.0334

5.6011

νCH(71)

13

2883

2650

2824

2710

114

5.0391

3601.83

0.3949

5.0901

8.7782

νCH(69)

14

2690

2612

2773

2754

19

124.41

560.612

0.75

6.0364

9.8682

νCH(45), νCH(59)

15

-

-

1763

1665

98

21.466

2728.8

0.0358

5.7656

9.2794

ν CH(59)

16

-

1937

1737

1652

85

100.03

607.442

0.327

4.8112

7.5584

ν CH(68), νCH(59)

17

-

-

1722

1632

90

36.787

21.835

0.3694

5.2171

8.0186

τRCCCC(45)

18

-

1823

1678

1615

63

47.271

76.3514

0.3699

2.1221

3.0029

τCCCC(11),τ2CCCC(45)

19

-

-

1669

1549

120

60.334

13.9519

0.3559

1.0992

1.5445

τac CC(43)

20

1735

-

1660

1544

116

14.089

242.346

0.3882

2.174

3.032

βipd CCC(43)

21

1712

1692

1652

1538

114

8.9211

39.0981

0.3059

1.0541

1.4578

τHCCC(10), τ2 HCCC(43)

22

1683

-

1634

1532

102

8.9246

27.6593

0.7207

1.7797

2.3705

ν CH(40)

23

1640

1623

1600

1503

97

32.644

43.8815

0.3352

1.5431

2.0263

τ HCCC(40), τ2 HCCC(13)

24

1610

1584

1564

1492

72

2.2286

213.605

0.75

2.7353

3.4868

βipd CCC(37), βipd CCC(14)

25

1578

1572

1508

1470

38

0.2645

241.023

0.4639

2.0129

2.3229

ν CC(33)

26

-

-

1499

1399

100

1.22

403.196

0.4473

1.7307

1.993

δHCC(33)

27

-

 

1480

1398

82

8.1576

41.2814

0.3305

1.9628

2.2066

ν CC(32)

28

-

-

1471

1381

90

0.3392

7.748

0.3303

1.6129

1.7843

ν CH(31), ν2CH(19)

29

1381

1362

1398

1370

28

4.2141

28.9577

0.2924

2.1216

2.299

τ HCCC(29), τ 2 HCCC(15)

30

1342

1321

1366

1356

10

39.397

20.6353

0.5409

3.7464

3.86

δCOC(29)

31

-

-

1358

1322

36

163.97

202.851

0.6478

2.099

2.1097

δCICC(22) ,δCICC(28)

32

1318

1300

1334

1306

28

27.417

607.619

0.376

2.4642

2.3205

ν CC(23) , ν2 CC(34)

33

1294

1285

1327

1264

63

2.1191

73.976

0.304

1.2226

1.105

ν CC(23)

34

1281

1266

1287

1238

49

1.2604

160.336

0.2754

1.1321

1.0117

ν CC(22)

34

1249

1252

1283

1231

52

48.352

323.027

0.3022

1.4881

1.2868

βHCC(18)

35

-

1235

1242

1211

31

46.428

229.473

0.4451

1.5723

1.3158

τ R2CCCC(18)

36

-

-

1231

1191

40

0.2944

9.3401

0.3076

1.2546

1.0026

τ RCCCC(39) , τ2R CCCC(19)

37

-

1201

1213

1164

49

9.8272

1.7765

0.3179

1.6512

1.2671

δOCCC(13)

38

1215

1213

1203

1141

62

6.8866

1.659

0.3497

1.7233

1.3141

ν CH(11) , ν2CH(13)

39

1207

1194

1198

   1137

57

26.837

7.6438

0.75

2.2871

1.6696

δHCC(23) , δHCC(13)

40

-

1187

1183

1113

70

104.3

12.22

0.6135

4.369

2.8532

βHCH(23)

41

-

-

1173

1052

121

12.328

0.0492

0.353

5.9102

3.679

βipd CCC(13)

42

1172

-

1162

1027

135

1.9548

357.685

0.2176

5.7932

3.6002

τ  RCCCC(22)

43

1132

1132

1123

1027

96

46.244

0.0466

0.2813

1.1466

0.709

τ HCCC(13)

44

1125

1113

1114

1008

106

4.0565

1.8511

0.75

1.3153

0.7888

βCCC(12)

45

1119

1105

1112

996

116

1.4003

0.6293

0.7498

1.3103

0.767

τ HCCC(12)

46

1089

998

1091

954

137

0.642

35.3366

0.75

1.9774

1.0614

τ RCCCC(12)

47

1081

963

1087

932

155

1.3584

0.5733

0.7497

1.3851

0.7093

βCCC(12)

48

1074

-

1083

931

152

4.8048

23.4977

0.5021

4.3495

2.2216

τ HCCC(10)

49

1071

947

1075

919

156

26.913

1.4612

0.75

1.524

0.7598

τ RCCCC()10

50

-

-

1040

905

135

4.3035

2.4844

0.7266

1.4884

0.7185

bHCC(10)

51

-

921

979

904

75

37.658

21.3403

0.5853

4.5931

2.2164

τ HCCC(11)

52

-

-

969

884

85

1.0979

7.8601

0.75

1.4935

0.6884

βCCCC(10)

53

-

907

954

815

139

52.182

1.6439

0.75

1.4915

0.584

τ HCCC (31), τ2 HCCC(10)

54

-

-

95

805

148

20.55

4.4528

0.75

1.4961

0.5717

ν OC(11)

55

872

832

831

785

46

0.2449

10.4039

0.1385

6.2195

2.2597

ν ClC(31)

56

-

-

816

715

101

39.672

0.0327

0.7499

1.9067

0.5756

βHCC(11)

57

856

815

801

713

88

46.755

0.874

0.2464

7.2344

2.171

ν ClC (11), βHCC(34)

58

841

796

759

702

57

0.2897

0.5042

0.75

2.1704

0.631

τ HCOC(10)

59

-

721

728

677

51

0.7455

7.974

0.4293

6.6003

1.7863

ν CC(10)

60

-

682

714

628

86

0.0126

0.3703

0.75

4.6218

1.076

βHCC(10)

61

672

-

647

585

62

23.488

1.5686

0.4693

4.9281

0.9958

τ RCCCC(11)

62

643

-

633

561

72

0.2659

0.3162

0.733

4.2091

0.7813

τ HCCC(10)

63

621

583

601

560

41

11.516

0.7849

0.2804

6.5422

1.2131

ν CH(10)

64

590

545

555

515

40

0.3552

1.698

0.3608

4.6916

0.7359

ν CH (11), νCH(25)

65

-

480

546

470

76

2.7885

0.0183

0.75

3.0372

0.3968

βCCC(10)

66

515

-

530

455

75

1.4285

0.1483

0.75

2.9843

0.364

τ HCCC(12)

67

-

432

476

444

32

4.0224

16.5656

0.3067

5.2709

0.6144

ν CC(10)

68

437

413

447

424

23

5.9169

8.6724

0.2962

9.6166

0.8797

βCCC(10)

69

411

410

415

419

12

1.6465

1.9902

0.3616

4.5785

0.2761

τ CCCC(10)

ν→Stretching, β→ Bending, τ→torsion, δ→Out-of-plane bending, βipd→in-plane bending, R→ring

 

4.3.1 Carbon-Hydrogen Vibrations

The C-H stretching is considered as characteristic Wavenumbers. Such differences are usually observed for C-H vibrations. The aromatic ring shows the occurrence of C-H stretching vibration modes in the range 3100-3000 cm-1 region [42, 43], which is the normal region for ready identification of C-H stretching vibrations. The title compounds observed C-H stretching vibration modes are assigned 3082,3053,3011,2984 cm-1 in FT-IR and 3079, 3060, 2983 cm-1in FT-Raman spectra. The Calculated scaled DFT/6311++G (d, p) and HF Values are 3103,3032,2710,2773 cm-1 and 3142,3078,2824,2754 cm-1 have been assigned to C-H stretching vibrations respectively.

4.3.2 Methyl group Vibrations

The Methyl group vibration modes for the assignments of CH3 group frequencies, fundamentally nine normal vibration modes can be associated to each Methyl group [44] namely, CH3 ss– symmetric stretch, CH3 ips– in-plane stretch , CH3 ops – out-of-plane stretch, CH3 ipb – in-plane bending , CH3 opb-out-of-plane bending , CH3 ops – out-of-plane stretch,CH3 ipr – in-plane rocking , CH3 opr-out-of-plane rocking; CH3 ipb – in-plane bending, CH3 out-of-plane bending modes, CH3 sb–symmetric bending, tCH3-twisting modes of CH3 group vibrations would be predictable to be depolarized for A'' symmetry species. The methyl C-H vibrations appear lower frequencies then aromatic C-H stretching vibrations.  The calculated Scaled DFT and HF of in-of-plane bending and out-of-plane bending modes of CH3 values are 3290,3276,3245 cm-1 and 3241,3226,3199 cm-1. The observed CH3 opb and ipb assigned 3182,3089,3001 cm-1 in FT-IR and 3179,3160,2996 cm-1 FT-Raman spectra. The CH3 group vibrations computed DFT and HF/6311++G (d, p) methods also show good agreement with recorded spectral data.

4.3.3 Chlorine -Carbon Vibrations

The characteristic Cl-C stretching mode has been assigned in the region 800-600 cm-1 [45]. The vibrations belonging to the bond between the benzene ring and halogen atoms were worth the discussion here, since mixing of several vibrations are possible due to the lowering of the molecular symmetry, and the occurrence of heavy atoms on the periphery of molecule [46]. The present calculations place the Cl-C group stretching modes at 872,856 cm-1 in FT-Raman and at 832,815 cm-1 in experimental FT-Raman spectrum of the molecule. The computational frequencies were identified in DFT at 831,801 cm-1 and 785, 713 cm-1 (HF) are assigned to Cl-C stretching vibration show good agreement with the earlier literature [47].

4.4 Nonlinear optical properties

Nonlinear optics properties 3C3'MS were calculated using the density functional theoretical method. Nonlinear       optical properties deal with the interaction of applied electric fields with different materials. The effect is established as generation of new electric fields that differ in phase, altered in frequency, amplitude or other physical properties [48]. The theoretical calculations have been shown to be useful in the description of the structure–property relationship between the polarizability and hyperpolarizabilities characterize the response of a molecular system in an applied electric field [49]. The theoretical methodology allows the determination of NLO properties as an inexpensive way to design molecules by studying their potential before synthesis and to determine the electronic structure and vibrational contributions to the high order hyperpolarizability of the molecular structure. Theoretical study plays an important role in understanding the molecular property relationship which is able to assistance in designing novel NLO materials. Theoretically, calculated values of polarizability (α) and hyperpolarizability (β) are shown in Table (4a) and (4b). The highest values of first hyperpolarizability (βtot) (2.705X10-24) is obtained in the method of HF/6-311++G (d, p) level using GAUSSIAN 09W package. It is interesting to note that the first hyperpolarizability of the title compound is twenty times that of the standard NLO material urea (0.13 ×10-30 esu) [50].

Table4 (a). Polarizability (x10-24esu) of the 3C3'MS molecule calculated at the DFT and HF method of 6- 311++G (d, p) level.         

*

DFT

HF

αxx

-95.4172

-98.2402

αxy

12.8560

14.9773

αyy

-97.7730

-98.4713

αxz

-0.0146

-0.0133

αyz

-0.0012

-0.0030

αzz

-111.9262

-115.0013

α

1.507X10-23

1.525X10-23

Δα

2.292X10-24

2.705X10-24

 

Table 4 (b) Hyperpolarizability β (x10-31esu) of the 3C3'MS molecule calculated at the DFT and HF method of 6- 311++G (d, p) level.

*

DFT

HF

βxxx

-277.8612

-291.9696

βxxy

30.1117

31.3506

βxyy

9.0819

9.2730

βyyy

2.4885

2.3886

βxxz

0.0575

0.0351

βxyz

-0.0232

-0.0216

βyyz

-0.0105

-0.0186

βxzz

-3.1948

0.0351

βyzz

0.0055

0.0809

βzzz

0.0165

0.0243

βii

2.366X10-30

2.459X10-30

 

4.5 UV-Vis Spectra Analysis

Time-dependent density functional theory (TD-DFT) calculation has been performed for 3C3'MS on the basis of completely optimized ground state molecular structure to investigate the electronic properties. The Molecules allow strong π−π* and σ –σ* electron transition in the UV-Vis range with high extinction coefficients. UV spectra analyses of 3C3'MS have been studied by computational method [51]. In order to recognize electronic transitions of the molecule, TD-DFT calculations on electronic absorption spectra in the different solvent (Acetonitrile, Methanol, Ethanol) were performed. The calculated results involving the frontier orbital energies, oscillator strengths (ƒ), absorption wavelengths (λ) and excitation energies (E) for different solvent (Acetonitrile, Methanol, Ethanol) phase are illustrated in Table (5a) and (5b) and the UV-Vis spectra of  3C3'MS is shown in Fig. 6. TD-DFT calculations expect three transitions in the near ultraviolent region for 3C3'MS molecule. As it can be seen from the UV–Vis spectra [52], absorption maximum values have been found to be 202, 241, 316 nm for Acetonitrile, 209, 241, 303 nm for Methanol, and 305,240, 206 nm Ethanol solution at TD-DFT/6-311++G (d, p) lavel theory. The absorption band of 3C3'MS at the longer observed peak at 316 nm is caused by the π−π* transition. Except for 316 nm, all the other absorption bands are mostly derived due to the observed transition from HOMO-LUMO is π−π*.

https://www.siftdesk.org/articles/images/558/6.png

Fig. 6 Simulated UV absorption spectra.

Table 5 (a). Computed excitation energies, electronic transition configurations and oscillator strengths (f) for the optical transitions with f > 0.01 of the absorption bands in visible and near- UV region for the 3C3'MS.

Solvent

Configurations composition (corresponding Transition orbitals)

Excitation Energy (eV)

 

Wave length

(nm)

Oscillator Strength (f)

Acetonitrile

63→65

64 → 65

3.85

321

0.5011

63→65

64 → 65

64 → 67

4.124

300

0.0006

62→ 65

63→ 66

64→66

4.56/

271

0.0093

Ethanol

63→ 65

64→ 65

4.07

304

0.7479

63→ 65

64→ 65

64→ 67

4.40

281

0.2559

62→65

63→ 66

64→ 66

4.60

269

0.0019

Methanol

 

63→ 65

64 → 65

4.07

304

0.7348

63 → 65

64 → 65

64 → 67

4.40

281

0.2599

62 → 65

63 → 66

64 → 66

4.60

269

0.0020

 

Table 5 (b) Calculated Maximum absorption wavelength (λmax), Oscillator Strength (ƒ), Excitation energy (eV) and Corresponding Electronic Transition for 3C3'MS.

Excited state

Wavelength λ (nm)

Excitation energy (cm-1)

Oscillator strength (f)

Major contributions

Acetonitrile

31097

321.5

0.7433

H->L (90%) H-1->L (9%)

33265

300.6

0.5011

H-1->L (85%), H->L (10%)

36853

271.3

0.0006

H-1->L (85%), H->L (10%)

40888

244.5

0.0093

H-3->L (35%), H-2->L (58%)

41357

241.7

0.2147

H-2->L (36%), H->L+1 (48%)

Ethanol

32852

304.4

0.7479

H->L (94%)

35517

281.5

0.2559

H-1->L (83%)

37143

269.2

0.0019

H-2->L (49%), H->L+1 (43%)

40738

245.4

0.0048

H-3->L (48%), H-2->L (40%)

41378

241.6

0.2903

H-2->L (32%), H->L+1 (46%)

Methanol

32894

304.0

0.7348

H ->L (94%)

35537

281.3

0.2599

H-1->L (82%)

37146

269.2

0.0020

H-2->L (49%), H->L+1 (43%)

40749

245.4

0.0045

H-3->L (45%), H-2->L (42%)

41396

241.5

0.2872

H-2->L (32%), H->L+1 (47%)

 

4.6 Molecular Electrostatic Potential

The MEP are useful 3D plots that can be used to visualize atomic charge distributions and charge related properties of studied compound, MEP surface map was computed at DFT/6-311++G (d, p) optimized geometries.  These maps are used as a reactivity displaying most possible sites for nucleophilic and electrophilic attacks. There are useful in biological application and non-covalent interactions particularly hydrogen bonds interactions [53, 54]. The surface is related to the molecular stability and is a very useful descriptor for determining the sites for electrophilic and nucleophilic reactions, the study of biological recognition processes and hydrogen bonding interactions. In addition, they provide information on the atomic charge related properties and atomic charge distribution of molecules. The MESP is an important parameter, and their study leads to a better understanding of complex biological processes involving the dipole–dipole, charge–dipole, and quadruple–dipole interactions. The electron total density onto which the molecular electrostatic surface map has been displayed in Figs. 7a and 7b, the electron density isosurface being 0.002 a.u. Figure reveals that negative regions (blue) are mostly localized over the O atoms for the electrophilic attack and the positive regions (green) are mainly localized in the Cl-atoms for a nucleophilic attack.

https://www.siftdesk.org/articles/images/558/7a.png

Fig. 7a Electrostatic potential contour map.

https://www.siftdesk.org/articles/images/558/7b.png

Fig. 7b Electrostatic potential contour map.

 

4.7 Natural Bonding Orbital’s

NBO analysis is a useful tool to investigate the highest possible percentage of the electron density between occupied Lewis-type (donor (i)) NBOs are thereby complemented by the unoccupied non-Lewis type (acceptor (j)) NBOs within the molecular system [55]. The delocalization effects can be recognized from the off-diagonal NBO Fock matrix elements of the second order Perturbation theory analysis. The interaction between occupancies of the bonding and weak occupancies of the valence anti-bonding molecular orbital energies can be qualitatively described in terms of NBO method that is expressed by means of second-order perturbation interaction energy  [55, 56]. In addition, Lewis-type (i) and non-Lewis type (j), the stabilization energy associated with i / j delocalization can be estimated as follows [56]:

https://www.siftdesk.org/articles/images/558/e1.png

Where  is the Lewis-type occupancy,   and  are diagonal elements and is the off diagonal NBO Fock matrix elements. The interaction between the  donor- acceptor and NBO Fock matrix elements [56, 57].

 

4.7.1 Second order Perturbation theory analysis: Donor-accepter interactions

The i - j interactions are considered by analyzing viable interactions between filled Lewis and empty non-Lewis NBOs, after approximating their molecular orbital energies through NBOs analysis. These energetic interactions are termed to as ‘delocalization’ corrections to the accurate possible natural Lewis structure. The potency of these delocalization interactions are relational to the NBO interacting intensities and molecular orbital energies which give important facts on the interactions among various parts of the molecules [58-60]. Some significant orbital intra-molecular hyper-conjugative interactions and corresponding NBO energies derived from the second order perturbation computation are listed in Table 6, which shows the most significant interactions between Lewis and non-Lewis orbital with C and O lone pairs.

Table 6. Second order perturbation theory analysis of Fock matrix of 3C3'MS by NBO method by DFT/6-311++G (d, p) method.

Donor (i)

Acceptor (j)

E(2)a kcal/mol

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

F(i,j)c a.u.

σ(2)C1-C2

π(3)C9

0.58

0.96

0.022

σ(2)C1-C2

σ*(2)C3-C4

13.71

0.29

0.060

σ(2)C3-C4

σ*(2)C5-C6

23.28

0.26

0.069

σ(2)C3-C4

σ*(2)C7-C8

18.48

0.27

0.065

σ(2)C5-C 6

σ*(2)C3-C4

19.17

0.29

0.068

σ (2)C7-C8

σ*(2)C3-C4

20.19

0.28

0.068

σ(2)C9-C10

σ*(2)C11-C12

23.21

0.26

0.071

CR (1)C14

π*(2)C9

1.69

11.22

0.123

nLP (2)O15

σ*(1)C5-C6

9.53

0.32

0.054

nLP (1)O15

σ*(1)C11-C12

6.56

1.10

0.076

nLP (2)O15

σ*(2)C11-C 12

29.01

0.32

0.092

σ*(2)C3-C4

σ*(2)C1-C2

64.23

0.02

0.064

σ*(2)C5-C6

σ*(2)C3-C4

228.3

0.01

0.080

σ*(2)C11- C12

σ*(2)C  9 - C  10

262.1

0.01

0.081

LR→ lone pair.

a Stabilisation (delocalisation) energy.

b Energy difference between i (donor) and j (acceptor) NBO orbitals.

c Fock matrix element i and j NBO orbitals.

The intra-molecular interaction is formed by the orbital overlap of bonding between σ (C-C) and anti-bonding σ*(C-C) orbital, which results that intramolecular charge (ICT) is causing stabilization of the system.NBO analysis has been performed on the 3C3'MS molecule at the DFT/6-311++G (d, p) level in order to elucidate, the intra-molecular rehybridization and delocalization of electron density within the molecule. The most important conjugative interactions in the title molecule involving lone pair LP(1) of O15 with σ*(C11-C12), σ*(C11-C12), and of σ*(C5-C6)  with the same result in the stabilization 9.53,6.56 and 29.01 kcal/mol, respectively, and also the lone pair LP(2) of the O15 with σ*(C11-C12) with the stabilization energy of 6.56 kcal/mol. As evident from Table 6, the hyperconjugative interaction due to the orbital overlap between σ bonding orbitals of σ(2)C3-C4, σ (2)C7-C8 ,σ(2)C9-C10 and σ* anti-bonding σ*(2)C5-C6,σ*(2)C3-C4 σ*(2) C11-C12 orbitals also results in the intra-molecular charge transfer contributing to stabilization of the molecular system [61].

 

 

4.8 Mulliken Atomic Charges

The natural population charge calculation plays an important role in the application of theoretical calculation to molecular structures [62], because the atomic charges affect the electronic structure, polarizability, and much more properties of the molecular systems. The Mulliken charge distributions of the title molecule have been calculated by methods DFT/6-311++G (d,p)  and HF/6-311++G(d,p)  methods with 6-311++G (d, p) levels of theory are collected in Table 7 and the better represent in graphical chart form as given Fig. 8. From the results, It is worthy to mention that C5, C11 and Cl17 atoms of 3C3'MS exhibit more positive charges than other H atoms in an aromatic ring and carbon atoms substituted by chloride group have highest atomic charges, while the O15 atom in the molecule have negative charges which form the C3, C6 and C9 atoms. The greater electronegative (ionic) character of negative charge on O atom and positive charge on Cl atom may suggest the formation of intermolecular bonding interaction in solid forms.

https://www.siftdesk.org/articles/images/558/8.png

Fig. 8 Mulliken population analysis chart.

Table 7. Mulliken atomic charge analysis of 3C3'MS.

Atoms

Atomic charge (ZA)

DFT

HF

C1

0.14848

-0.16586

C2

-0.15002

-0.16995

C3

0.09345

-0.02588

C4

-0.14415

-0.17174

C5

0.24273

0.30057

C6

-0.09192

-0.15322

C7

-0.13293

-0.20061

C8

-0.12662

-0.17687

C9

0.09242

-0.01098

C10

-0.18336

-0.24651

C11

0.27876

0.39479

C12

-0.12752

-0.22523

C13

-0.14593

-0.19343

C14

-0.12971

-0.19495

O15

-0.56349

-0.77017

C16

-0.16982

-0.13623

CI17

0.05863

0.07367

H18

0.12574

0.19628

H19

0.12629

0.19665

 

4.9 Molecular properties

The HOMO and LUMO energy values are useful descriptors in studying global reactivity of molecules and chemical hardness (h), chemical potential (µ), electronegativity (χ), electrophilicity index (ω) and softness (S). The chemical Hardness (h) is defined within the computational method as the total energy (E) with respect to the number of electrons (E) as external potential property of the system that measures both the global descriptors and molecular stability of the molecules [63].

https://www.siftdesk.org/articles/images/558/e2.png

Using Koopman’s theorem for closed-shell molecules [64], ionization potential (IP), electron affinity (EA), chemical potential, chemical hardness and softness, electrophilicity index as well as electronegativity defined [65]. The HOMO and LUMO orbital energies as IP and EA are related to the energy values of the EHOMO and ELUMO can be expressed as:     

https://www.siftdesk.org/articles/images/558/e3.png  

https://www.siftdesk.org/articles/images/558/e4.png

https://www.siftdesk.org/articles/images/558/e5.png

https://www.siftdesk.org/articles/images/558/e6.png

Where IP and EA, Chemical Hardness (ƞ) and softness (S) [66] are known as global reactivity descriptors [67, 68] and have been theoretically justified within the background of DFT and TD-DFT [64]. These chemical descriptors-based parameters are commonly used to measure chemical reactivity and molecular properties [69]. Chemical hardness basically deals with the physical polarization of the electron cloud of the ions or molecules and atoms under small perturbation during a molecular properties and chemical reactivity [70]. Generally, soft molecules have a smaller value and the hard molecules have a larger EHOMO and ELUMO energy gap value [71, 72]. The computed values of the hardness, softness, chemical potential, electronegativity, and electrophilicity index, IP of donor and EA of acceptor have been calculated and the results are presented in Table 1.

 

https://www.siftdesk.org/articles/images/558/9.png

Fig. 9 Experimental and theoretical 13C NMR spectra.

https://www.siftdesk.org/articles/images/558/10.png

Fig. 10 Experimental and theoretical 1H NMR spectra.

 

4.10 NMR Spectra analysis

The theoretical values for 1H and 13C NMR Chemical shift of 3C3'MS have been compared with the excellent agreement with experimental data are listed in Table 8. The structural parameters are obtained with the DFT and HF/6-311++ G (d, p) level of theory and it is used to predict 1H and13C chemical shifts with the recommended GIAO approach [73] and TMS is used for reference. The experimental and theoretical NMR spectra of the 3C3'MS molecule is shown in Figs. 9 and 10 respectively. Aromatic carbon peaks are observed from 160.01 to 56 ppm and calculated values by DFT and HF methods range from 156 to 17 and 142 to 12 ppm. The carbon atoms C16, C12, C14, C10, C8, C6, C13 and C3 are recognized to downfield NMR signals 160.01,141,139,136,130,130 and 128. These reveal the presence of partially positive charge on the carbon atoms [74]. The chemical shift (δ) value provides information on the chemical environment/magnetic properties of the protons.  Protons next to electron donating groups are shielded and protons next to electron withdrawing groups are deshielded [75]. The proton numbered H30 has the maximum chemical shift value 7.5 ppm. The 30H to 27H downfield is observed in the experimental values in 1H with respect to calculated values. All computations are in good agreement with experimental data.  

Table 8. NMR Chemical shift (13C and 1H) of 3C3'MS [δ (ppm)].

 

Atoms

 

Experimental

 

DFT

 

HF

16C

160

156

142

12C

141

142

140

14C

139

140

138

10C

136

140

137

8C

130

138

131

6C

130

138

122

13C

128

130

114

3C

56

17

12

30H

7.5

7.5

7.0

24H

7.3

7.5

6.8

20H

7.3

7.3

6.7

21H

7.2

7.2

6.6

25H

7.1

6.8

6.5

26H

7.0

6.7

6.5

19H

3.8

2.4

5.8

27H

-

0.6

1.9

 

4.11 Natural Charge Analysis

Natural charges and electron population charge analysis [76] have been important role in the application of density functional calculation of molecular system. The difference of charge magnitude is in proportion with the natural charges, but they differ appreciably because this analysis includes number of core, valance and Rydberg electrons located in diffuse orbital. The development of atomic charges on the separate atom and the accumulation of electrons in the valance, core and Rydberg sub-shells are shown in Table 9. In the most electronegative charge of 0.52278 is accumulated on the oxygen atom O6 and -0.23811is accumulated on the carbon atom C4. Usually the electron cloud between bonded atoms is symmetrical, when the two atoms are similar but if one of atoms has a greater tendency to attract the electron cloud then it shifts slightly towards that atom. According to an electrostatic point of new of the molecule, these electronegative atoms have a tendency to donate an electron. Whereas, the most electropositive atoms such as; H10 have a tendency to accept an electron [77]. Further, the natural population analysis showed that 128 electrons in the 3C3'MS molecule is distributed on the sub shells as follows:

Core: 41.98304 (99.9596% of 42)

Valance: 85.81491 (99.7848% of 86)

Rydberg: 0.20205 (0.1579% of 128)

 

Table 9. Natural Population analysis of 3C3'MS.

 

Atoms

 

Charge (e)

Natural population (e)

 

Total (e)

Core

Valence

Rydberg

C1

-0.19571

1.99898

4.18647

0.01026

6.19571

C2

-0.21423

1.99897

4.20489

0.01036

6.21423

C3

-0.05348

1.99893

4.04248

0.01208

6.05348

C4

-0.23811

1.99878

4.2282

0.01113

6.23811

C5

-0.01624

1.99843

4.00026

0.01754

6.01624

O6

-0.52278

1.99972

6.51755

0.00551

8.52278

C7

-0.3559

1.99927

4.34998

0.00666

6.3559

Cl8

-0.04686

9.99981

7.04005

0.00701

17.04686

H9

0.22932

0.0073

0.76918

0.0015

0.77068

H10

0.23071

0.0002

0.76783

0.00146

0.76929

 

4.12 Thermodynamic analysis

Thermodynamic analysis is important for understanding the chemical processes. The theoretical calculation is a well-established and efficient tool to calculate various statistical thermodynamic properties of molecular system. Nowadays, due to theoretical predictions of thermodynamic properties, and their experimental measurements are possible with high accuracy. The thermodynamic functions such as enthalpy change, heat capacity and molar entropy can be predicted easily from the molecular partition function. These calculations are used to convert molecular energy levels into macroscopic properties. Molecular energy arises from electronic excitation, Molecular translation, rotation, and vibration. This information establishes the spectroscopy of the molecule of interest [78, 79]. In the present studies, the parameters such as SCF energies, specific heat capacities, rotational constants, zero-point vibrational energies, dipole moments, rotational temperatures, 3C3'MS have been calculated at DFT and HF method with 6-311++G(d,p) basis set are listed in Table 10.

Table 10. Theoretically computed zero-point vibrational energy (Kcal mol−1), rotational constants (GHz), rotational temperatures (Kelvin), thermal energy (Kcal mol−1), molarcapacity at constant volume (cal mol−1 Kelvin−1), dipole moment (Debye) and vibrational temperatures (Kelvin) for 3C3'MS.

Parameter

DFT/B3LY

HF

 

Zero-point vibrational energy

Rotational constant (GHZ)

 

 

Rotational temperature (Kelvin)

 

 

Energy total (KCal/Mol)

Translational(KCal/Mol)

Rotational(KCal/Mol)

Vibrational(KCal/Mol)

Dipole moment

Vibrational temperature (Kelvin)

 

 

150.66513

1.41876

0.12322

0.11345

0.06809

0.00591

0.00544

160.108

0.889

0.889

158.331

3.7721

11.21

70.14

78.14

99.35

142.91

225.55

267.41

285.17

290.92

336.66

362.21

380.06

434.12

460.29

566.91

639.98

654.65

677.52

 

 

160.36038

1.41876

0.12322

0.11345

0.06809

0.00591

0.00544

168.481

0.889

0.889

166.704

3.7290

90.53

129.94

164.14

219.61

251.23

258.08

315.80

338.57

416.53

433.71

439.60

493.59

511.64

597.74

629.37

686.24

763.73

785.62

 

 

Conclusion

In this study, comparing the theoretical FT-IR, FT-Raman and Experimental FT-IR, FT-Raman spectra of the title compound 3C3'MS have been recorded. The investigations on fundamental modes along with structural, thermodynamic, electronic analysis, Natural population analysis and Mulliken population analysis of the compound have been made using ab initio DFT and HF methods with 6-311++G(d,p) basis sets. Close agreement is observed in the molecular geometries like bond lengths and bond angles calculated by DFT and HF methods. The UV-Vis spectra analysis of the molecule was also carried out. Theoretical 13C and 1H chemical shift values are reported and compared with experimental data, showing a very good agreement both for 13C and 1H. The HOMO–LUMO energy gap helped in analyzing the chemical reactivity of the molecule. Global hardness, softness and electrophilicity were calculated.  The FMOs have been pictured and the HOMO–LUMO energy gap has been calculated. First hyperpolarizability analysis reveals that the title compound possesses considerable NLO properties. The NBO analysis have been made with which the chemical stability and intra molecular interactions have been interpreted and the transactions give stabilization to the structure have been identified by second order perturbation energy calculations. The ESP map shows that the negative potential sites are on oxygen as well as the positive potential sites are the hydrogen and chlorine atom in a molecule.

Acknowledgement

The authors are thankful to the learned referees for their useful and critical comments, which improved the quality of the manuscript. One of the authors, M. Prakasam, acknowledges Periyar University for financial support in the form of a University Research Fellowship (URF).


Abbreviations

3C3'MS

3-Chloro-3'-Methoxystilbene

RHF

Restricted Hartree-Fock

MP2

Moller-Plesset second order perturbation theory

NMR

Nuclear Magnetic Resonance

ICT

Intramolecular change transfer

HOMO

Highest occupied molecular orbital

LUMO

Lowest unoccupied molecular orbital

DFT

Density Functional Theory

IVR

Intramolecular Vibrational Redistribution

References

  1. J. Saltiel, J. D.Agostino, E. D. Megarity, L. Metts, K. R. Neuberger, M. Wrighton, O. C. Zafiriou, O.L. Chapman, The cis-trans Photoisomerization of Olefins Marcel Dekker, New York, 1973.

  2. D. H. Waldeck, Chem. Rev. 1991, 91, 436.

    View Article           
  3. H. Meier, Angew. Chem. Int. Ed. Engl. 1992, 31, 1540.

    View Article           
  4. J. S. Baskin, L. Banares, S. Pedersen, A. H. Zewail, J. Phys. Chem. 1996, 100, 11933.

    View Article           
  5. P. Senthilkumar, C. Nithya and P. M. Anbarasan. J. Mol. Mod. 2013, 19, 4573. PMid:23959394

    View Article      PubMed/NCBI     
  6. K.A. Muszkat, Top. Curr. Chem. 1980, 88, 143

  7. T. Nakabayashi, H. Okamoto, M. Tasumi, J. Phys. Chem. 1998, 102, 9695

    View Article           
  8. S. L. Schultz, J. Qian, J.M. Jean, J. Phys. Chem. 1997, 101, 1006.

    View Article           
  9. R. J. Sension, A. Z. Szarka, R.M. Hochstrasser, J. Chem. Phys. 1992, 97, 5242.

    View Article           
  10. J. K. Rice, A. P. Baronavski, J. Phys. Chem. 1992, 96, 3366.

    View Article           
  11. H. Sanei, A. Asoodeh, S. Hamedakbari-Tusi, J. Chamani, J Solu. Chem. 2011, 40, 1905.

    View Article           
  12. P. Mokaberi, V. Reyhani, Z. Amiri-Tehranizadeh, M. R. Saberi, S. Beigoli, F. Samandar and J. Chamani, New J Chem. 2019, 43, 8132.

    View Article           
  13. Z. Sharif-Barfeh, S. Beigoli, S. Marouzi, A. Sharifi Rad, A. Asoodeh, J. Chamani, J. Sol. Chem. 2017, 46, 488.

    View Article           
  14. M. Zolfagharzadeh, M. Pirouzi, A. Asoodeh, M.R. Saberi and J. Chamani, J. Biomol. Struc. Dynam. 2014, 32, 1936. PMid:24125112

    View Article      PubMed/NCBI     
  15. J. Grundy, Chem. Rev. 1957, 57, 356.

    View Article           
  16. K. Hagiwara, N. Kosaka, Y. Yoshioka, R. Takahashi ,F. Takeshita & T. Ochiya, Sci. Rep. 2012, 2, 314. PMid:22423322

    View Article      PubMed/NCBI     
  17. H. A. Ali, K. Kondo, Y. Tsuda, Chem. Pharm. Bull. 1992, 40, 1136.

  18. H. Matsuda, N. Tomohiro, K. Hiraba, S. Harima, S. Ko, K. Matsuo, M. Yoshikawa, M. Kubo, Bio. Pharm. Bull. 2001, 24, 267. PMid:11256482

    View Article      PubMed/NCBI     
  19. S. Sanoh, S. Kitamura, K. Sugihara, N. Fujimoto, S. Ohta, J. Heal. Sci. 2003, 49, 367.

    View Article           
  20. K. Tsumura, K. Furuya, A. Sakamoto, Mo. Tasumi, J. Raman Spectrosc. 2008, 39, 1591.

    View Article           
  21. A. Weigel, N. P. Ernsting, J. Phys. Chem. B 2010, 114, 7893. PMid:20481560

    View Article      PubMed/NCBI     
  22. R. K. Chaudhuri, J. Phys. Chem. A 2013, 117, 9434. PMid:23530611

    View Article      PubMed/NCBI     
  23. A. L. Houk, I. L. Zheldakov, T. A. Tommey, and C. G. Elles, J. Phys. Chem. B 2015, 119, 9344. PMid:25369524

    View Article      PubMed/NCBI     
  24. M. Arivazhagan, V. Krishnakumar, J. Xavier, G. Ilango, V. Balachandran, Spectrochimi. Acta Part A 2009, 72, 946. PMid:19196545

    View Article      PubMed/NCBI     
  25. R. G.W .Yang, Density Functional Theory of Atoms and Molecular, Oxford, New York, 1989.

  26. R. O .Jones, O. Gunnarson, Rev.Mol.Phys. 1989, 61, 689

    View Article           
  27. T. Ziegier, Chem. Rev. 1991, 91, 651.

    View Article           
  28. W. Kohn, L. J .Sham, Phys. Rev. A 1965, 140, 1133.

    View Article           
  29. A. D. Becke, Phys. Rev. Part A 1988, 38, 3098 PMid:9900728

    View Article      PubMed/NCBI     
  30. C .T. Lee, W.T. Yang, R.G. Parr, Phys. Rev. Part B. 1988, 37, 785. PMid:9944570

    View Article      PubMed/NCBI     
  31. J. Frisch, G.W. Trucks, H.B .Schlegel, G.E .Scuseria, M.A. Robb, J.R .Cheeseman, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, R. Nakajima, Y. Honda, O. Kilao, H. Nakai, T. Verven, J. A. Montgomery Jr., J. E .Peralta, F. Ogliaro, M .Bearpark, J.J .Heyd, E. Brothers, K. N. Kudin, V. N. Staroveror, R. Kobayashi, J. Normand, K. Ragavachari, A .Rendell, J. C. Burant, S .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. Strattmann, O .Yazyev, A.J. Austin, R. Cammi, J.W. Ochetrski, R.L. Martin, K. Morokuma, V. G. Zakrazawski, G .A. Votn, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J. B. Foresman, Gaussian O. G., Revision A.O2 Gaussian Inc., Wallingford, CT, 2009.

  32. A. D .Becke, J. Chem. Phys. 1993, 98, 5652.

    View Article           
  33. C. Lee, W. Yang, R. C .Parr, J. Phys. Rev. B 1998, 37, 789.

  34. T. Sundius, J. Mol. Struct. 1990, 218, 326. 80287-T

    View Article           
  35. Computer program Gauss View 3.09, Ver. 2 Gaussian Inc, PA, Pittsburgh, 2008.

  36. P. Pulay, G. Fogarasi, F. Pang, J. E. Boggs, J. Am. Chem. Soc. 1979, 10, 2550.

    View Article           
  37. G. Keresztury, J.M. Chalmers, P.R. Griffth, Raman Spectroscopy: Theory in Handbook of Vibrational Spectroscopy, John Wiley & Sons Ltd., New York, 2002.

  38. M.S. Alam, D .U. Lee, J. Mol. Struc. 2017, 1128, 185.

  39. M. Bakiler, I.V. Maslov, S. Akyuz, J. Mol. Struct. 1999, 475, 83. 00491-8

    View Article           
  40. J. S. Murray, K .Sen, Elsevier, Amsterdam, the Netherlands, 1996.

  41. J. Chamani, M. Heshmati, J Coll. Interf. Sci. 2008, 322, 119. PMid:18405913

    View Article      PubMed/NCBI     
  42. V. Krishnakumar, N .Prabavathi, Spectrochim. Acta Part A 2009, 72, 747. PMid:19121975

    View Article      PubMed/NCBI     
  43. G.Varsanyi, Academic Kiaclo, Budapest, 1973.

  44. P.S. Kalsi, Sectroscopy of Organic Compounds New Age International P Limited Publishers, New Delhi, 2005.

  45. V. Balachandran, G. Santhi, V. Karpagam, A. Lakshmi, Spectrochim. Acta Part A 2013, 110, 140. PMid:23562743

    View Article      PubMed/NCBI     
  46. R. A. Yadav, I .S .Sing, Indian J. Pure Appl. Phys. 1985, 23, 627.

  47. K. Parimala, V. Balachandran, Spectrochim. Acta Part A 2011, 81, 723. PMid:21795105

    View Article      PubMed/NCBI     
  48. Y. R. Shen, the Principles of Nonlinear Optics Wiley, New York, 1984.

  49. P. Vennila, M . Govindaraju, G .Venkatesh, C . Kamal, J. Mol. Struct. 2016, 1111, 156.

    View Article           
  50. M. Adant, L. Dupuis, L .Bredas, Int. J. Quantum Chem. 2004, 56, 507.

  51. B. M. Wong, M. Piacenza, F. Della Sala, Phys. Chem. Chem. Phys. 2009, 11, 4508. PMid:19475168

    View Article      PubMed/NCBI     

Journal Recent Articles