Journal of Theoretical & Computational Science

Journal of Theoretical & Computational Science
Open Access

ISSN: 2376-130X

Review Article - (2014) Volume 1, Issue 2

Experimental [FT-IR and FT-Raman] Analysis and Theoretical [IR, Raman, NMR and UV-Visible] Investigation on Propylbenzene

S Xavier1,2, S Ramalingam3* and S Periandy4
1Department of Physics, St. Joseph College of Arts and Science, Cuddalore, Tamil Nadu, India, E-mail: puduvaixavier@gmail.com
2Barathiyar University, Coimbathore, Tamilnadu,, India, E-mail: puduvaixavier@gmail.com
3Department of Physics, AVC College, Mayiladuthurai, Tamil Nadu, India, E-mail: puduvaixavier@gmail.com
4Department of Physics, Tagore Arts College, Puducherry, India, E-mail: puduvaixavier@gmail.com
*Corresponding Author: S Ramalingam, Department of Physics, AVC College, Mayiladuthurai, Tamil Nadu, India, Tel: + 04364225367, Fax: +04364225367 Email:

Abstract

In the present methodical study, FT-IR, FT-Raman and NMR spectra of the Propylbenzene were recorded and the fundamental vibrational frequencies were tabulated and assigned. The Gaussian hybrid computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-311+G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were compared with experimental values. The change of chemical environment of present compound due to the addition of Ethyl and methyl chain was studied. Moreover, 13C NMR and 1H NMR were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts related to TMS were compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The calculated HOMO and LUMO energies (kubo gap) were displayed in the figures which show that the occurring of charge transformation within the molecule. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. NLO properties related to Polarizability and hyperpolarizability was also discussed. The local reactivity of the molecule has been studied using Fukui function.

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Keywords: Propylbenzene, Gauge independent atomic orbital, Chemical shifts, FMO, Fukui function

Introduction

Propylbenzene is an organic compound that is based on the aromatic hydrocarbon with an aliphatic substitution. It is inflammable and colorless liquid, insoluble in water and less dense than water. The chemical is also flammable and incompatible with strong oxidizing agents. It is stable, but may form peroxides in storage if in contact with the air. It is important to test for the presence of peroxides before heating or distilling. Other synonyms of Propylbenzene are: n-Propylbenzene; Isocumene; Propylbenzene; 1-Phenylpropane; 1-Propylbenzene; Phenyl propane; Benzene, n-propyl. When there is contact between aromatic hydrocarbons and strong oxidizing agents it amounts to vigorous reactions sometimes amounting to explosions. They can react exothermically with bases and with diazo compounds. Substitution at the benzene nucleus occurs by halogenations (acid catalyst), nitration, sulfonation, and the Friedel-Crafts reaction.The propylbenzene is a byproduct while alkylation of benzene with propylene and it is useful a starting material for chemical synthesis [1]. Moreover, DIPB can be dehydrogenated to di-isopropenylbenzenes which can further be applied to produce plastics, elastomers and resins with valuable properties [2].

The literature survey reveals that, to the best of our knowledge, no intensive observation of spectroscopic [FT-IR and FT-Raman] and theoretical [HF/DFT] investigation has been reported so far. Therefore, the present investigation was undertaken to study the vibrational spectra, geometrical frame work review, inter and intra molecular interaction between HOMO and LUMO energy levels and first order hyperpolarizability of non linear optical (NLO) activity of the molecule.

Experimental Details

The compound Propylbenzene is purchased from Sigma–Aldrich Chemicals, USA, which is of spectroscopic grade and hence used for recording the spectra as such without any further purification. The FT-IR spectrum of the compound is recorded in Bruker IFS 66V spectrometer in the range of 4000–400 cm−1. The spectral resolution is ±2 cm−1. The FT-Raman spectrum of same compound is also recorded in the same instrument with FRA 106 Raman module equipped with Nd:YAG laser source operating at 1.064 μm line widths with 200 μW power. The spectra are recorded in the range of 4000–100 cm−1 with scanning speed of 30 cm−1min−1 of spectral width 2 cm−1. The frequencies of all sharp bands are accurate to ±1 cm−1.

Computational Methods

In the present work, HF and some of the hybrid methods; B3LYP and B3PW91 are carried out using the basis sets 6-31+G(d,p) and 6-311+G(d,p). All these calculations are performed using GAUSSIAN 09W [3] program package on Pentium IV processor in personal computer. In DFT methods; Becke’s three parameter hybrids function combined with the Lee-Yang-Parrcorrelation function (B3LYP) [4,5], Becke’s three parameter exact exchange-function (B3) [6] combined with gradient-corrected correlational functional of Lee, Yang and Parr (LYP) [7,8] and Perdew and Wang (PW91) [9,10] predict the best results for molecular geometry and vibrational frequencies for moderately larger molecules. The calculated frequencies are scaled down to give up the rational with the observed frequencies. The scaling factors are 0.959, 1.028, 1.297 for HF/6-311++G(d,p). For B3LYP/6-311+/6- 311++G(d,p) basis set, the scaling factors are 0.993, 0.810/0.994,1.046, 1.09. For B3PW91/6-31+G/6-311+G(d,p) basis set, the scaling factors are 0.983, 1.04,1.08/1.01, 0.940,0.794. The optimized molecular structure of the molecule is obtained from Gaussian 09 and Gaussview program and is shown in Figure 1. The comparative optimized structural parameters such as bond length, bond angle and dihedral angle are presented in Table 1. The observed (FT-IR and FT-Raman) and calculated vibrational frequencies and vibrational assignments are submitted in Table 2. Experimental and simulated spectra of IR and Raman are presented in the Figures 2 and 3.

theoretical-computational-science-Molecular-Structure-Propylbenzene

Figure 1: Molecular Structure of Propylbenzene.

theoretical-computational-science-Experimental-Calculated-spectra

Figure 2: Experimental [A] and Calculated [B,C & D] FT-IR spectra of Propylbenzene.

theoretical-computational-science-Experimental-spectra-Propylbenzene

Figure 3: Experimental [A] and calculated [B,C&D] FT-Raman spectra of Propylbenzene.

Geometrical parameter HF/ 6-311+G(d,p) HF/ 6-311++G (d,p) B3LYP/ 6-311 +G (d,p) B3LYP/ 6-311++G(d, p) B3PW91/ 6-311+G(d,p) B3PW91/ 6-311++G(d,p)
Bond length(Å)
C1-C2 1.390 1.390 1.399 1.399 1.393 1.397
C1-C6 1.385 1.386 1.393 1.393 1.388 1.391
C1-H7 1.076 1.007 1.085 1.085 1.085 1.086
C2-C3 1.390 1.390 1.399 1.399 1.393 1.397
C2-C12 1.513 1.513 1.512 1.512 1.507 1.507
C3-C4 1.385 1.385 1.393 1.393 1.388 1.391
C3-H8 1.076 1.076 1.085 1.085 1.085 1.086
C4-C5 1.385 1.385 1.393 1.394 1.388 1.391
C4-H9 1.075 1.075 1.084 1.084 1.083 1.085
C5-C6 1.385 1.585 1.394 1.394 1.388 1.391
C5-H10 1.075 1.075 1.084 1.084 1.083 1.085
C6-H11 1.075 1.075 1.084 1.084 1.083 1.085
C12-C13 1.535 1.535 1.541 1.541 1.533 1.535
C12-H17 1.087 1.087 1.095 1.095 1.094 1.096
C12-H18 1.087 1.087 1.095 1.095 1.094 1.096
C13-H14 1.087 1.087 1.095 1.095 1.094 1.096
C13-C15 1.527 1.527 1.530 1.530 1.524 1.525
C13-H16 1.087 1.087 1.095 1.095 1.094 1.096
C15-H19 1.086 1.086 1.093 1.093 1.092 1.093
C15-H20 1.087 1.087 1.094 1.094 1.093 1.095
C15-H21 1.087 1.087 1.094 1.094 1.093 1.095
Bond Angle(º)
C2-C1-C6 121.024 121.024 121.059 121.057 121.010 121.049
C2-C1-H7 119.540 119.540 119.350 119.383 119.350 119.352
C6-C1-H7 119.434 119.434 119.638 119.558 119.638 119.598
C1-C2-C3 118.182 118.181 118.247 118.145 118.247 118.158
C1-C2-C12 120.903 120.902 120.861 120.909 120.861 120.908
C3-C2-C12 120.903 120.904 120.865 120.922 120.865 120.906
C2-C3-C4 121.024 121.025 121.010 121.056 121.010 121.049
C2-C3-H8 119.540 119.539 119.351 119.386 119.351 119.352
C4-C3-H8 119.435 119.434 119.638 119.556 119.638 119.598
C3-C4-C5 120.201 120.200 120.131 120.144 120.131 120.143
C3-C4-H9 119.750 119.751 119.814 119.799 119.814 119.799
C5-C4-H9 120.047 120.048 120.053 120.055 120.053 120.055
C4-C5-C6 119.366 119.367 119.469 119.452 119.469 119.455
C4-C5-H10 120.316 120.316 120.265 120.273 120.265 120.271
C6-C5-C10 120.316 120.315 120.265 120.273 120.265 120.271
C1-C6-C5 120.201 120.200 120.131 120.143 120.131 120.143
C1-C6-H11 119.751 119.751 119.814 119.800 119.814 119.799
C5-C6-H11 120.047 120.047 120.053 120.055 120.053 120.056
C2-C12-C13 113.214 113.218 112.942 113.225 112.942 112.984
C2-C12-H17 109.311 109.310 109.552 109.515 109.552 109.546
C2-C12-H18 109.312 109.314 109.550 109.518 109.550 109.551
C13-C12-H17 109.148 109.144 109.045 108.940 109.045 109.060
C13-C12-H18 109.149 109.145 109.046 108.941 109.046 109.057
H17-C12-H18 106.483 106.486 106.495 106.474 106.495 106.426
C12-C13-H14 109.131 109.131 108.989 108.972 108.989 108.944
C12-C13-C15 112.702 112.701 112.693 112.872 112.693 112.893
C12-C13-H16 109.133 109.132 108.990 108.972 108.990 108.941
H14-C13-C15 109.686 109.689 109.921 109.842 109.9213 109.926
H14-C13-H16 106.295 109.294 106.103 106.102 106.103 105.970
C15-C13-H16 109.685 109.686 109.921 109.845 109.921 109.922
C13-C15-H19 111.070 111.065 111.376 111.269 111.376 111.322
C13-C15-H20 111.212 111.213 111.180 111.258 111.180 111.297
C13-C15-H21 111.211 111.211 111.181 111.261 111.181 111.295
H19-C15-H20 107.732 107.741 107.685 107.655 107.685 107.614
H19-C15-H21 107.732 107.741 107.684 107.655 107.684 107.613
H20-C15-H21 107.699 107.699 107.548 107.552 107.548 107.501
Dihedral Angle (º)
C6-C1-C2-C3 -0.2286 -0.2368 -0.1521 -0.1869 -0.1521 -0.1666
C6 -C1-C2-C12 178.5556 178.5336 178.0406 178.1085 178.0406 177.9944
H7-C1-C2-C3 179.5007 179.5038 179.5501 179.5035 179.5501 179.5225
H7-C1-C2-C12 -1.7151 -1.7257 -2.2572 -2.2012 -2.2572 -2.3165
C2-C1-C6-C5 0.0739 0.0838 0.0302 0.0399 0.0302 0.0255
C2-C1-C6-H11 179.829 179.8267 179.776 179.7575 179.776 179.747
H7-C1-C6-C5 -179.6557 -179.6572 -179.6712 -179.6499 -179.6712 -179.6628
H7-C1-C6-H11 0.0994 0.0858 0.0746 0.0677 0.0746 0.0587
C1-C2-C3-C4 0.2286 0.2368 0.1525 0.1871 0.1525 0.1667
C1-C2-C3-H8 -179.4989 -179.5024 -179.5501 -179.5054 -179.5501 -179.5221
C12-C2-C3-C4 -178.5556 -178.5336 -178.0401 -178.1081 -178.0401 -177.9944
C12-C2-C3-H8 1.7169 1.7272 2.2573 2.1995 2.2573 2.3169
C1-C2-C12-C13 -89.3641 -89.3567 -89.0743 -89.0714 -89.0743 -89.0769
C1-C2-C12-H17 32.5395 32.5431 32.6862 32.7195 32.6862 32.7267
C1-C2-C12-H18 148.7309 148.7389 149.165 149.1335 149.165 149.1201
C3-C2-C12-C13 89.3802 89.3802 89.071 89.1765 89.071 89.0334
C3-C2-C12-H17 -148.7094 -148.7201 -149.1686 -149.0326 -149.1686 -149.1631
C3-C2-C12-H18 -32.518 -32.5243 -32.6898 -32.6186 -32.6898 -32.7696
C2-C3-C4-C5 -0.074 -0.0838 -0.031 -0.0404 -0.031 -0.0257
C2-C3-C4-H9 -179.8288 -179.8268 -179.7766 -179.759 -179.7766 -179.7468
H8-C3-C4-H9 179.6539 179.6557 179.6707 179.6516 179.6707 179.6622
H8-C3-C4-H9 -0.1009 -0.0873 -0.0749 -0.0671 -0.0749 -0.0589
C3-C4-C5-C6 -0.0862 -0.0751 -0.0942 -0.1109 -0.0942 -0.1189
C3-C4-C5-H10 -179.8106 -179.8093 -179.8245 -179.8336 -179.8245 -179.8281

Table 1: The optimized geometrical parameters of propylbenzene.

S. No Symmetry Species C s Observed Frequency(cm-1) Methods Vibrational  Assignments
FT-IR FT-Raman HF B3LYP B3PW91
6-311+G (d, p) 6-311+G (d, p) 6-311++G (d, p) 6-311+G (d, p) 6-311++G (d, p)
1 A′ 3090w -     3093 3097 3095 3090 3096 (C-H) υ
2 A′ 3080m - 3080 3084 3082 3079 3083 (C-H) υ
3 A′ - 3070m 3071 3076 3073 3070 3075 (C-H) υ
4 A′ - 3060m 3059 3063 3060 3057 3062 (C-H) υ
5 A′ - 3040s 3056 3062 3059 3056 3060 (C-H) υ
6 A′ 3030s - 2976 2997 2994 2998 3006 (C-H) υ
7 A′ - 3010w 2973 2994 2991 2993 3001 (C-H) υ
8 A′ 3005w 3005w 2956 2972 2970 2973 2979 (C-H) υ
9 A′ 2960s   2937 2951 2949 2954 2958 (C-H) υ
10 A′   2940s 2927 2937 2935 2935 2938 (C-H) υ
11 A′ 2930s - 2920 2931 2930 2930 2931 (C-H) υ
12 A′ - 2870m 2912 2928 2925 2927 2929 (C-H) υ
13 A′ 1610w - 1653 1596 1596 1621 1605 (C=C) υ
14 A′ 1605w 1605m 1628 1578 1575 1599 1584 (C=C) υ
15 A′ 1590w 1590m 1524 1513 1558 1490 1478 (C=C) υ
16 A″ 1500s - 1505 1499 1503 1461 1454 (CH3) α
17 A′ 1495s - 1491 1486 1490 1448 1443 (C-C) υ
18 A′ 1455m - 1442 1484 1442 1440 1436 (C-C) υ
19 A′ 1450s - 1436 1476 1434 1438 1430 (C-C) υ
20 A′ - 1440w 1428 1421 1429 1433 1428 (C-C) υ
21 A′ 1380w - 1374 1353 1361 1363 1354 (C-C) υ
22 A′ 1340w 1340w 1352 1325 1333 1323 1330 (C-C) υ
23 A′ - 1290w 1315 1305 1312 1293 1316 (C-H)  δ
24 A′ - 1280w 1277 1286 1294 1267 1306 (C-H)  δ
25 A′ - 1250w 1272 1267 1275 1253 1273 (C-H)  δ
26 A′ - 1200s 1221 1262 1203 1253 1262 (C-H)  δ
27 A′ - 1190w 1181 1196 1193 1186 1201 (C-H)  δ
28 A′ - 1180w 1170 1175 1172 1174 1188 (C-H)  δ
29 A′ 1160w 1160w 1150 1152 1149 1142 1157 (C-H)  δ
30 A′ 1105w - 1100 1132 1129 1117 1137 (C-H)  δ
31 A′ 1100w - 1106 1094 1075 1100 1069 (C-H)  δ
32 A′ 1095w 1095w 1077 1078 1059 1094 1057 (C-H)  δ
33 A′ 1050w - 1051 1041 1023 1051 1019 (C-H)  δ
34 A′ 1040w - 1032 1022 1004 1036 1007 (C-H)  δ
35 A′ 1030w - 1024 1010 993 1032 1002 (C-C)  δ
36 A′ - 1000s 1018 990 972 1001 968 (C-C)  δ
37 A′ 910w   943 974 952 997 913 (C-C)  δ
38 A″ 895w - 929 956 937 979 902 (C-H) γ
39 A″ 890w 890w 882 868 886 895 896 (C-H) γ 
40 A″ - 865w 824 835 855 839 871 (C-H) γ
41 A″ - 840w 814 821 841 815 846 (C-H) γ
42 A″ 820w 820 806 798 815 802 826 (C-H) γ
43 A″ 740vs 740vs 757 770 788 771 760 (C-H) γ
44 A″ 705vs - 710 711 727 714 700 (C-H) γ 
45 A″ 700vs - 682 697 713 691 682 (C-H) γ
46 A″ - 610m 664 665 649 666 655 (C-H) γ
47 A″ 590s 590w 583 594 580 591 581 (C-H) γ 
48 A″ 570vs   550 559 546 558 547 (C-H) γ
49 A″ 530vw   505 493 542 496 489 (C-H) γ
50 A′ 490s - 418 410 442 404 398 (CCC) δ
51 A′ 480s - 341 343 370 337 332 (CCC) δ
52 A′ 470vw - 305 307 330 302 299 (CCC) δ
53 A″ 400 m - 278 276 297 271 266 (CCC)  γ
54 A″ 370m   238 227 245 225 222 (CCC)  γ
55 A″ 280s - 103 101 109 99 98 (CCC)  γ
56 A″ 270s - 84 82 89 82 80 (C-C)  γ
57 A″ 260s _- 37 45 48 38 43 (C-C)  γ

Table 2: Observed and calculated vibrational frequencies of propylbenzene using HF and DFT (B3LYP & B3PW91) at the 6-31+& 6-311+G (d, p) level.

The 1H and 13C NMR isotropic shielding are calculated with the GIAO method [11] using the optimized parameters obtained from B3LYP/6-311++G(d,p) method. 13C isotropic magnetic shielding (IMS) of any X carbon atoms is made according to value 13C IMS of TMS, CSX=IMSTMS-IMSx. The 1H and 13C isotropic chemical shifts of TMS at B3LYP methods with 6-311++G(d,p) level using the IEFPCM method in DMSO, Nitromethene and CCl4. The absolute chemical shift is found between isotropic peaks and the peaks of TMS [12]. The electronic properties; HOMO-LUMO energies, absorption wavelengths and oscillator strengths are calculated using B3LYP method of the time-dependent DFT (TD-DFT) [13,14] method in gas phase and solvent phase. Moreover, the dipole moment, nonlinear optical (NLO) properties, linear polarizabilities and first hyperpolarizabilities have also been studied. The local reactivity of the molecule has been studied using Fukui function. The condensed softness indices are found and it is used to predict both the reactive centers and possible sites of nucleophilic and electrophilic attacks.

Results and Discussion

Molecular geometry

The molecular structure of Propylbenzene belongs to CS point group symmetry. The optimized structure of the molecule is obtained from Gaussian 09 and Gauss view program [15] and is shown in Figure 1. The present molecule contains two ethyl and one methyl groups which are loaded in the left moiety. The hexagonal structure of the benzene is broken at the point of substitution due to the addition of heavy mass. It is also evident that, the bond length (C1-C2&C2-C3) at the point of substitution is 0.059Å is greater than rest of others in the ring. Consequently, the property of the same also changed with respect to the ligand (ethyl and methyl groups). The bond angle of C1-C2-C3 is 1.306º elevated than C4-C5-C6 in the ring which also conform the breaking of hexagonal shield.

The structure optimization and zero point vibrational energy of the compound in HF and DFT(B3LYP/B3PW91) with 6-311+/6-311+G(d,p) are 123.00, 115.69, 115.679, 116.943,and 115.89 Kcal/Mol, respectively.The calculated value of HF is greater than the values of DFT method because the assumption of ground state energy in HF is greater than the true energy. Though, both C loaded by CH2, the bond length values between C2-C12 and C12-C13 are differed 0.0290 Å since further weighted by CH3 in the chain. The entire C-H bonds in the chain and methyl group having almost equal inter nuclear distance. Form the optimized molecular structure; it is observed that there is no arithmetical change in the chain. So there is no further change in geometrical property.

Vibrational assignments

In order to obtain the spectroscopic signature of the propylbenzene, the computational calculations are performed for frequency analysis. The molecule, has CS point group symmetry, consists of 21 atoms, so it has 57 normal vibrational modes. On the basis of Cs symmetry, the 57 fundamental vibrations of the molecule can be distributed as 39 in-plane vibrations of A′ species and 18 out of plane vibrations of A″ species, i.e., Γvib = 39 A′ + 18 A″. In the CS group symmetry of molecule is non-planar structure and has the 57 vibrational modes span in the irreducible representations.

The harmonic vibrational frequencies (unscaled and scaled) calculated at HF, B3LYP and B3PW91 levels using the triple split valence basis set along with the diffuse and polarization functions, 6-31+/6-311++G(d,p) and observed FT-IR and FT-Raman frequencies for various modes of vibrations have been presented in Tables 2 and 3. Comparison of frequencies calculated at HF andB3LYP/B3PW91 with the experimental values reveal the over estimation of the calculated vibrational modes due to the neglect of a harmonicity in real system. Inclusion of electron correlation in the density functional theory to certain extends makes the frequency values smaller in comparison with the HF frequency data. Reduction in the computed harmonic vibrations, although basis set sensitive is only marginal as observed in the DFT values using 6-311+G (d,p).

S. No. Observed    frequency Calculated frequency
HF B3LYP B3PW91
6-311+G (d, p) 6-31+G (d, p) 6-311+G (d, p) 6-31+G (d, p) 6-311+G (d, p)
1 3090w 3347 3187 3187 3211 3198
2 3080m 3333 3174 3174 3199 3185
3 3070m 3323 3166 3165 3190 3176
4 3060m 3310 3152 3152 3176 3163
5 3040s 3307 3151 3151 3175 3161
6 3030s 3220 3084 3084 3115 3105
7 3010w 3217 3081 3081 3110 3100
8 3005w 3199 3059 3058 3089 3077
9 2960s 3178 3037 3037 3069 3055
10 2940s 3167 3023 3023 3050 3035
11 2930s 3160 3017 3017 3044 3028
12 2910m 3151 3013 3012 3041 3025
13 1610w 1789 1643 1643 1684 1658
14 1605w 1762 1622 1622 1661 1636
15 1590w 1649 1525 1525 1548 1527
16 1500s 1629 1510 1510 1518 1502
17 1495s 1614 1497 1497 1505 1491
18 1455m 1614 1495 1495 1503 1488
19 1450s 1607 1487 1487 1501 1482
20 1440w 1598 1482 1482 1496 1479
21 1380w 1537 1411 1411 1423 1403
22 1340w 1513 1382 1382 1402 1378
23 1290w 1471 1361 1361 1371 1363
24 1280w 1429 1342 1342 1343 1353
25 1250w 1423 1322 1322 1328 1319
26 1200s 1366 1316 1316 1328 1308
27 1190w 1321 1248 1248 1257 1244
28 1180w 1309 1226 1226 1244 1231
29 1160w 1287 1202 1202 1210 1199
30 1105w 1231 1181 1181 1184 1178
31 1100w 1199 1124 1124 1132 1122
32 1095w 1168 1108 1108 1126 1110
33 1050w 1139 1070 1070 1082 1070
34 1040w 1119 1050 1050 1066 1057
35 1030w 1110 1038 1038 1062 1052
36 1000s 1104 1017 1017 1030 1016
37 910w 1097 1001 996 1026 995
38 895w 1081 982 980 1007 980
39 890w 1026 929 927 949 926
40 865w 959 894 894 912 900
41 840w 947 879 879 886 874
42 820w 938 854 853 872 853
43 740vs 881 824 824 838 826
44 705vs 826 761 760 776 761
45 700vs 794 746 746 751 741
46 610m 772 712 712 724 712
47 590s 678 636 636 642 632
48 570vs 640 598 599 606 595
49 530vw 547 507 507 515 505
50 490s 452 413 414 420 411
51 480s 369 346 346 350 343
52 470vw 330 309 309 314 309
53 400 m 301 278 278 282 275
54 370m 258 229 229 234 229
55 280s 112 102 102 103 101
56 270s 91 83 83 85 83
57 260s 40 45 45 40 44

Table 3: Calculated unscaled frequencies of propyl benzene using HF/DFT (B3LYP&B3PW91) with 6-31+(d,p) and 6-311+G(d,p) basis sets.

C-H Vibrations: The C–H stretching vibrations are normally observed in the region 3100–3000 cm−1 for aromatic benzene structure [16,17] which shows their uniqueness of the skeletal vibrations. The bands appeared at 3090, 3070, 3065, 3060 and 3040 cm−1 in the Propylbenzene have been assigned to C–H ring stretching vibrations. The C–H in-plane ring bending vibrations are normally occurred as a number of strong to weak intensity bands in the region 1300-1000 cm−1 [18]. In the present case, four C–H in-plane bendingvibrations of the present compound are identified at 1290, 1280, 1250 and 1200 cm 1. The calculated frequencies for B3LYP/6-31++G (d,p) and B3LYP/6- 311++G (d, p) methods for C–H in-plane bending vibrations showed excellent agreement with recorded spectrum as well as literature data. The C–H out-of-plane bending vibrationsare normally observed in the region 1000–809 cm−1 [19]. The C–H out of plane bending vibrations is observed at 895, 890, 865, 840 and 820 cm−1. The entire C-H stretching and bending vibrations are located at the top end of the expected region which is because of these vibrations have not affected by ethyl and methyl group in the molecule. Whereas, all the out of plane bending vibrations are suppressed to the lower end of the expected region.

Methyl groups vibrations: With the aromatic ring, for the substitution of CH3 group, the vibrational frequencies for nine fundamental vibrations such as three stretching, in plane and out of plane bending vibrations normally observed in the region of 3000- 2750 cm-1, 1250-950 cm-1 and 950- 720 cm-1 [19,20], respectively.

Accordingly, the stretching vibrational peaks are observed at 3030, 3010 and 3005 cm-1, in plane bending vibrational bands are found at 1180, 1160, and1105 cm-1 and out of plane bending signals are identified at 740, 705 and 700 cm-1. All the CH3 stretching vibrations are located in asymmetric range which shows the enhancement of CH3 group vibrations in the present molecule. Except, two out of plane vibrations, the entire bending signals are received within the expected region. The ethyl group in the chain influences the bending vibrations of CH3. The above assignments go along with the literature of R.N. Singh and Varsanyi [19,20].

Ethyl group vibrations: The aliphatic chain substitution CH2 ethyl group with the aromatic ring will have eight fundamental vibrations such as four stretching, in plane and out of plane bending vibrations normally found in the region of 3000 -2850, 1300-1000 cm-1 and 810- 722 cm-1 [21,22], respectively. In the present study of propylbenzene the stretching vibrations are observed at 2960,2930, 2910, 2870 cm-1 , the in-plane bending vibrations are found at 1100, 1095, 1050, 1040 cm-1 and subsequently out of plane vibrations are at 610, 590, 570 and 530 cm-1. All the stretching and bending vibrational bands are found within the region.

C-C vibrations: The bands due the C-C stretching vibrations are called skeletal vibrations normally observed in the region 1430 - 1650 cm-1 for the aromatic ring compounds [23,24]. Socrates [25] mentioned that, the presence of conjugate substituent suchas C=C causesstretching peaks around the region 1625-1575 cm-1. As predicted in the earlier references, in this title compound,the prominent peaks are found with strong and medium intensity at 1610, 1605 and 1590 cm-1 due to C=C stretching vibrations. The C-C stretching vibrations are appeared at1495, 1455 and1450 cm-1. The CCCin-plane and out of plane bending vibrations are appeared at 490, 480 and 470 cm-1 and 400, 370 and 280 cm-1. Similar to the ring C-H vibrations, these skeletal CC stretching and bending vibrations are found within the expected region and also make a good agreement with literature [26].

NMR assessment: NMR spectroscopy is currently used for structure elucidation of complex molecules. The combined use of experimental and computationaltools offers a powerful gadget to interpret and predict the structure of bulky molecules. The optimized structure of Propylbenzene is used to calculate the NMR spectra at B3LYP method with 6-311++G(d,p) level using the GIAO method and the chemical shifts of the compound are reported in ppm relative to TMS for 1H and 13C NMR spectra which are presented in Table 4. The corresponding spectra are shown in Figure 4.

Atom position Gas Solvent
Chloroform DMSO
  B3LYP/6-311+G(d,p) (ppm) B3LYP/6-311+G (2d,p) GIAO (ppm) Shift (ppm) B3LYP/6-311+G(d,p) (p­­­­­pm) B3LYP/6-311+G(2d,p) GIAO (ppm) Shift (ppm) B3LYP/6-311+G(d,p) (ppm) B3LYP/6-311+G(2d,p) GIAO (ppm) Shift (ppm)
C1 50.6257 131.84 81.2143 50.6257 131.84 81.2143 50.2521 132.214 81.9619
C2 35.1536 147.312 112.1584 35.1536 147.312 112.1584 33.6205 148.845 115.2245
C3 52.5577 129.908 77.3503 52.5577 129.908 77.3503 52.2505 130.215 77.9645
C4 48.1658 134.3 86.1342 48.1658 134.3 86.1342 48.155 134.31 86.155
C5 51.9287 130.537 78.6083 51.9287 130.53 78.6013 52.2318 130.234 78.0022
C6 48.5706 133.89 85.3194 48.5706 133.89 85.3194 48.5497 133.916 85.3663
C12 142.636 39.8297 102.8063 142.636 39.8297 102.8063 142.899 39.5661 103.3329
C13 167.62 14.846 152.774 167.62 14.846 152.774 167.836 14.6298 153.2062
C15 169.06 13.4059 155.6541 169.06 13.4059 155.6541 169.613 12.8531 156.7599
7H 24.3718 7.5103 16.8615 24.3718 7.5103 16.8615 24.1899 7.6922 16.4977
8H 24.1444 7.7377 16.4067 24.1444 7.7377 16.4067 23.9782 7.9039 16.0743
9H 24.286 7.5961 16.6899 24.286 7.5961 16.6899 24.1354 7.7467 16.3887
10H 24.4747 7.4074 17.0673 24.4747 7.4074 17.0673 24.3433 7.5388 16.8045
11H 24.2974 7.5847 16.7127 24.2974 7.5847 16.7127 24.1446 7.7375 16.4071
14H 30.66 1.2221 29.4379 30.66 1.2221 29.4379 30.628 1.2541 29.3739
16H 31.0626 0.8195 30.2431 31.0626 0.8195 30.2431 31.0074 0.874 30.1334
17H 30.2216 1.6605 28.5611 30.2216 1.6605 28.5611 30.1511 1.731 28.4201
18H 29.2452 2.6369 26.6083 29.2452 2.6369 26.6083 29.191 2.6911 26.4999
19H 31.0626 0.8219 30.2407 31.0602 0.8219 30.2383 31.064 0.8181 30.2459
20H 32.0056 -0.1235 32.1291 32.0056 -0.1235 32.1291 31.9903 -0.1082 32.0985
21H 31.1101 0.772 30.3381 31.1101 0.772 30.3381 31.0941 0.788 30.3061

Table 4: Experimental and calculated 1H and 13C NMR chemical shifts (ppm) of propylbenzene.

theoretical-computational-science-spectra-Propylbenzene-Solvant

Figure 4: 1H and 13C NMR spectra of Propylbenzene in Gas and Solvant phase.

In view of the range of 13C NMR chemical shifts for similar organic molecules usually is >100 ppm [27,28] the accuracy ensures reliable interpretation of spectroscopic parameters. In the present work, 13C NMR chemical shifts of some carbons in the chain are >100 ppm, as they would be expected in Table 5. In the case of Propylbenzene, the chemical shift of C1, C3, C3,C4, C5 and C6 are 81.21, 77.35, 86.13, 78.60, and 85.31 ppm, respectively. The shift is higher in C2, C12, C13 and C15 than rest of others.

λ(nm) E (eV) ( f ) Major contribution Assignment Region Bands
Gas  
234.96 5.276 0.0048 HL (92%) n→π* Quartz UV R-band (German, radikalartig)
210.53 5.889 0.0162 HL (89%) n→π* Quartz UV
205.88 6.0220 0.0015 HL (86%) n→π* Quartz UV
DMSO  
234.72 5.282 0.0082 HL-1 (90%) n→π* Quartz UV R-band (German, radikalartig)
210.99 5.876 0.0258 HL-1 (90%) n→π* Quartz UV
201.57 6.150 0.0022 HL-1 (87%) n→π* Quartz UV
      H+1L-1 (83%) σ→σ* Quartz UV
CCl4  
235.13 5.273 0.0082 HL-1 (86%) n→π* Quartz UV R-band (German, radikalartig)
211.41 5.864 0.0252 HL-1 (85%) n→π* Quartz UV
204.13 6.0736 0.0020 HL-1 (78%) n→π* Quartz UV
      H+1L-1(77%) σ→σ* Quartz UV
Nitro methyl  
234.70 5.282 0.0080 H+1L (86%) n→π* Quartz UV R-band (German, radikalartig)
210.93 5.878 0.0252 H+1L-1 (85%) n→π* Quartz UV
201.59 6.150 0.002 HL-1 (78%) n→π* Quartz UV
      H+1L-1(74%) σ→σ* Quartz UV

Table 5: Theoretical electronic absorption spectra of propylbenzene (absorption wavelength λ (nm), excitation energies E (eV) and oscillator strengths (f)) obtained using the TD-DFT/B3LYP/6-311++G(d,p) method.

The C3 in the chain has more shifted than other due to the delocalization of σ and π electrons. The shift of the entire carbons of the ring is found increased when going from gas to solvent due to the solvent effect. The shift values of carbons in DMSO phase are greater than Chloroform phase. The chemical shift values of oxygen have not changed due to the solvent effect. The experimental and theoretical 1H and 13C NMR chemical shift of Propylbenzene are presented in Table 5. This effect of isolation is the main cause to change the chemical property from benzene to Propylbenzene.

Optical properties (HOMO-LUMO analysis)

The UV and visible spectroscopy is used to detect the presence of chromophores in the molecule and whether the compound has NLO properties or not. The calculations of the electronic structure of Propylbenzene are optimized in singlet state. The low energy electronic excited states of the molecule are calculated at the B3LYP/6- 311++G(d,p) level using the TD-DFT approach on the previously optimized ground-state geometry of the molecule. The calculations are performed for Propylbenzenein gasphase and with the solvent of DMSO, CCl4, and Nitromethene. The calculated excitation energies, oscillator strength (f) and wavelength (λ) and spectral assignments are given in Table 6.

f+ = (q+1)-q f-=q-(q-1) Δf=(f+)-(f-) ΔS =Δfσgs Δω=Δfωgei
-0.0990 5.5674 -5.6665 -64.971 -0.3539
0.10410 -1.0720 1.1761 13.4852 0.0734
-0.0989 5.57436 -5.6732 -65.049 -0.3544
-0.0488 -3.9275 3.8786 44.472 0.2422
-0.1308 0.4939 -0.6248 -7.1641 -0.0390
-0.0487 -3.9281 3.8793 44.480 0.2423
-0.0636 -3.1527 3.0890 35.419 0.1929
0.03984 -0.0434 0.0832 0.9542 0.0051
-1.1396 -0.7127 -0.4268 -4.8945 -0.0266

ΔS = local softness, σgs- global softeness; -Δω local electophilic index, ωgei- global
electrophilic index

Table 6: Fukui function and global and local softness, and electrophilicity index of propylbenzene.

TD-DFT calculations predict three transitions in the quartz ultraviolet region. In the case of gas phase, the strong transition is at 234.96, 210.53 and 205.88nm with an oscillator strength f=0.0048, 0.0162, 0.0015 with 5.2767 eV energy gap. The transition is n→π* in visible and quartz ultraviolet region. The designation of the band is R-band(German, radikalartig) which is attributed to above said transition of prophyl groups. They are characterizes by low molar absorptivities (ξmax<100) and undergo hypsochromic shift with an increase in solvent polarity. The simulated UV-Visible spectra in gas and solvent phase of Propylbenzene are shown in Figure 5.

theoretical-computational-science-Visible-Propylbenzene-Solvant

Figure 5: UV Visible spectra of Propylbenzene in Gas and Solvant Phase.

In the case of DMSO solvent, strong transitions are 234.72, 210.99, 201.57 nm with an oscillator strength f=0.0082, 0.0258, 0.0022 nm with maximum energy gap 6.1509 eV.They are assigned to n → π* and σ→ σ*transitions and belongs to quartz ultraviolet region. This shows that, from gas to solvent, the transitions moved from visible to quartz ultraviolet region. This view indicates that, the Propylbenzene molecule having crystal property and thus, it is capable of having rich NLO properties. In addition to that, the calculated optical band gap 5.111 eV which ensure that the present compound has NLO properties. In view of calculated absorption spectra, the maximum absorption wavelength corresponds to the electronic transition from the HOMO to LUMO with maximum contribution.

The chemical hardness and potential, electronegativity and Electrophilicity index are calculated and their values are shown in Table 7. The chemical hardness is a good indicator of the chemical stability. The chemical hardness is decreased slightly (1.72-3.01) in going from Gas to solvent. Hence, the present compound has much chemical stability. Similarly, the electronegativity is increased from 3.45 upto 3.36, from Gas to solvent, if the value is greater than 1.7; the property of bond is changed from covalent to ionic. Accordingly, the bonds in the compound converted from covalent to ionic and are independent of solvent. Electrophilicity index is the measure of energy lowering due to maximal electron flow between donor [HOMO] and acceptor [LUMO]. From the Table 7, it is found that the Electrophilicity index of Propylbenzene is 3.45 in gas and 3.36 in solvent, which is moderate and this value ensure that the strong energy transformation between HOMO and LUMO.The dipole moment in a molecule is another important electronic property. Whenever the molecule has larger the dipole moment, the intermolecular interactions are very strong. The calculated dipole moment value for the title compound is 12.24 Debye in gas and 15.75 in solvent. It is too high which shows that; the Propylbenzene molecule has strong intermolecular interactions.

Parameters Gas CCl4 Nitromethene DMSO
EHOMO (eV) -6.63169 -5.25427 -6.824886218 -6.82679
ELUMO (eV) -0.39865 -0.4928 -0.572527435 -0.57443
ΔEHOMO-LUMO gap (eV) -6.23304 -4.76147 -6.252358783 -6.25236
Electronegativity (χ) 3.5151 2.380736 3.126179391 3.126179
Chemical hardness (η) -3.11652 -2.38074 -3.126179391 -3.12618
Global softness (σ) -0.32087 -0.42004 -0.319879276 -0.31988
Electrophilicity index (ω) -1.98346 -1.19037 -1.563089696 -1.56309
Dipole moment (μ) 15.44518 17.7527 21.17546183 20.47384

Table 7: HOMO, LUMO, Kubo gap, global electronegativity, global hardness and softness, global electrophilicity index of propylbenzene.

Global softness and local region-selectivity

Molecular charge distribution, molecular orbital surfaces and HOMO and LUMO energies have been used as reactivity descriptors in DFT study. The energy gap between the HOMO and LUMO orbital have been found to be adequate to study the stability and chemical reactivity of great variety of molecular system and is an important stability index. Besides the traditional reactivity descriptors there are a set of chemical reactivity descriptors which can be derived from DFT, such as global hardness (η), global softness, local softness (S), Fukui function (f) and global and local electrophilicity indexes (ω) [29-39]. These quantities are often defined by the Koopman’s theorem [40,41].

Electronegativity (χ) is the measure of the power of an electron or group of atoms to attract electrons towards itself [42] and according to Koopman’s theorem; it can be estimated by using the following equation:

equation(1)

Where EHomo is the energies of the highest occupied molecular orbital (HOMO) and ELumo is the energy of the lowest unoccupied molecular orbital (LUMO).Global hardness (η) measures the resistance of an atom to a charge transfer [41] and it is estimated using the equation:

equation(2)

Global softness (S) describes the capacity of an atom or group of atoms to receive electrons [43] and it is estimated by using the equation:

equation(3)

Where, η is the global hardness values. Global electrophilicity index (ω) is estimated by using the electronegativity and chemical hardness parameters through the equation:

equation(4)

A high value of electrophilicity describes a good electrophile while a small value of electrophilicity describes a good nucleophile.

Fukui indices are a measurement of the chemical reactivity, as well as an indicator of the reactive regions and the nucleophilic and electrophilic behaviors of the molecule. The regions of a molecule where the Fukui function is large are chemically softer than the regions where the Fukui function is small, and by invoking HSAB principle in a local sense, one may establish the behavior of different sites with respect to hard or soft reagents. Condensed to atom Fukui function is reactive descriptor to identify nucleophilic and electrophilic attack site in candidate molecules, perhaps it is also used to recognize the electron acceptor center and donor centers. fk+ for any given site is positive then it is a preferred site for nucleophilic attack, on the contrary negative value implies electrophilic attack.

The Fukui function is defined as [44,45]:

equation(5)

Where ρ(r) is the electron density and N

equation(6)

N is the number of electrons and r is the external potential exerted by the nucleus.

Phenyl ring gets activated at ortho and para positions as there are electron releasing substituent such as -OH, -NH2, -OR, R, etc. Propyl substituent in fact is an electron releasing substituent, consequently promotes the ortho and para positions for electrophilic attack a common reactivity trend observed in phenyl compounds. Local reactivity descriptors such as fk+,fk-, Δf, Δω for the different sites of phenyl ring are in conformity with the observed reactivity trend of the candidate molecule.

fk+,fk-, Δf, Δω unambiguously reveal the nucleophilic attack to be in the decreasing sequence asC6>C4 >C2 and that of electrophilic attack is found to be in the order C1>C3>C5 in the phenyl ring. This trend for attack of electrophile is in conformity with that of ΔS and Δω. The ortho and para positions show the tendency for attack of electrophile which is indeed a common trend observed in alkyl substituted phenyl ring compounds.

Molecular electrostatic potential (MEP) maps

The molecular electrical potential surfaces illustrate the charge distributions of molecules three dimensionally. This map allows us to visualize variably charged regions of a molecule. Knowledge of the charge distributions can be used to determine how molecules interact with one another and it is also be used to determine the nature of the chemical bond.Molecular electrostatic potential is calculated at the B3LYP/6-311+G(d,p) optimized geometry [46,47]. There is a great deal of intermediary potential energy, the non red or blue regions indicate that the electro negativity difference is not very great. In a molecule with a great electro negativity difference, charge is very polarized, and there are significant differences in electron density in different regions of the molecule. This great electro negativity difference leads to regions that are almost entirely red and almost entirely blue [48]. Greater regions of intermediary potential, yellow and green, and smaller or no regions of extreme potential, red and blue, are key indicators of a smaller electronegativity.

The color code of these maps is in the range between -6.15 a.u. (Deepest red) to 6.15 a.u. (deepest blue) in compound. The positive (blue) regions of MEP are related to electrophilic reactivity and the negative (green) regions to nucleophilic reactivity shown in Figure 6. From the MEP map of the candidate molecule the red regions of the molecule found to be ready for electrophilic attack, and especially in the phenyl ring the atoms are clouded with red colour. From the findings of the Fukui local reactivity descriptor the atoms C1, C3 and C5 are nucleophile ready for electrophilic attack and atoms C2, C4 and C6 are the regions for nucleophilic attack. Molecular electrostatic potential map can be confirmed with the finding of the Fukui descriptors.

theoretical-computational-science-map-propylbenzene

Figure 6: MEP map of propylbenzene.

Polarizability and first order hyperpolarizability calculations

In order to investigate the relationships among molecular structures and non-linear optic properties (NLO), the polarizabilities and first order hyperpolarizabilities of the Propylbenzene compound was calculated using DFT-B3LYP method and 6-311+G(d,p) basis set, based on the finite-field approach.

The Polarizability and hyperpolarizability tensors (Table 8) (αxx, αxy, αyy, αxz, αyz, αzz and βxxx, βxxy, βxyy, βyyy, βxxz, βxyz, βyyz, βxzz, βyzz, βzzz) can be obtained by a frequency job output file of Gaussian. However, α and β values of Gaussian output are in atomic units (a.u.). So they have been converted into electronic units (esu) (α; 1 a.u.=0.1482×10−24esu, β; 1 a.u.=8.6393×10−33 esu). The calculations of the total molecular dipole moment (μ), linear polarizability (α) and first-order hyperpolarizability (β) from the Gaussian output have been explained in detail previously [49,50] and DFT has been extensively used as an effective method to investigate the organic NLO materials [51-55].

Parameter a.u. Parameter a.u.
αxx - 53.3963 βxxx 13.79
αxy -0.2807 βxxy 0.9912
αyy -52.6869 βxyy 3.7575
αxz -0.9506 β yyy 0.8982
αyz -0.2339 βxxz 0.4223
αzz -59.5384 βxyz 0.6611
αot -55.2072 βyyz -0.7173
Δα 6.695 βxzz -9.9781
μx -0.5586 βyzz -1.0315
μy - 0.0696 βzzz 1.4772
μz 0.0731 βtot 2.940
μot 0.1611    

Table 8: The electronic dipole moment (μ) (Debye), polarizability (α) and first hyperpolarizability (β) of propylbenzene.

equation(7)

equation(8)

equation(9)

In Table 7, the calculated parameters described above and electronic dipole moment {μi(i = x, y, z) and total dipole moment μtot } for title compound are listed. The total dipole moment was calculated using the following equation [56].

equation(10)

It is well known that, molecule with high values of dipole moment, molecular Polarizability, and first hyperpolarizability having more active NLO properties. The first hyperpolarizability (β) and the component of hyperpolarizability βx, βy and βz of Propylbenzene along with related properties (μ0, αtotal, and Δα) are reported in Table 6. The calculated value of dipole moment is found to be 0.16111 Debye. The highest value of dipole moment is observed for component μX. In this direction, this value is equal to 0.0731 D. The lowest value of the dipole moment of the molecule compound is μY component (-0.0696 D). The calculated average Polarizability and anisotropy of the Polarizability is -55.2077×10-24 esu and 6.6956×10−24 esu, respectively. The magnitude of the molecular hyperpolarizability β, is one of important key factors in a NLO system. The B3LYP/6-311+G(d,p) calculated first hyperpolarizability value (β) is 2.9780×10−30 esu. From the above results, it is observed that, the molecular Polarizability and hyperpolarizability of the title compound in all coordinates are active. So that, the Propylbenzene can be used to prepare NLO crystals and those crystal is able to produce second order harmonic waves.

Conclusion

In the present investigation, FT-IR, FT-Raman and 13C NMR and 1H NMR spectra of the Propylbenzene were recorded and the observed vibrational frequencies were assigned depending upon their expected region. The chronological change of finger print and group frequency region of the amino acid with respect to the functional group has also monitored. The change of geometrical parameters along with the substitutions was deeply analyzed. The simulated 13C NMR and 1H NMR were compared with the recorded spectrum and the chemical shifts related to TMS were studied. The change of chemical properties of the molecule by the substitutions has been analysed. The electrical and optical properties of the Propylbenzene were profoundly investigated using frontier molecular orbital (Figure 7). From the UVVisible spectra, it was found that the present compound was optically active and posses NLO properties. The molecular electrostatic potential (MEP) map was performed and from which the change the chemical properties of the compound was also discussed. The possible sites of nucleophilic and electrophilic attacks in the molecule were determined through local reactivity and Fukui condensed softness indices.

theoretical-computational-science-Frontier-Molecular-Orbitals

Figure 7: Frontier Molecular Orbitals of Propylbenzene.

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Citation: Xavier S, Ramalingam S, Periandy S (2014) Experimental [FT-IR and FT-Raman] Analysis and Theoretical [IR, Raman, NMR and UV-Visible] Investigation on Propylbenzene. J Theor Comput Sci 1:109.

Copyright: © 2014 Xavier S, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
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