Spectrochimica Acta Part A 79 (2011) 962969

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

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

FT-IR and FT-Raman, vibrational assignments, molecular geometry, ab initio (HF) and DFT (B3LYP) calculations for 1,3-dichlorobenzene
D. Mahadevan a, , S. Periandy b , S. Ramalingam c
a b c

Department of Physics, Govt. Arts College, Tindivanam, Tamilnadu, India Department of Physics, Tagore Arts college, Puducherry, India Department of Physics, A.V.C. College, Mayiladuthurai, Tamilnadu, India

a r t i c l e

i n f o

a b s t r a c t
The FT-IR and FT-Raman vibrational spectra of 1,3-dichlorobenzene (1,3-DCB) have been recorded using Bruker IFS 66 V Spectrometer in the range 4000100 cm1 . A detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The optimized molecular geometry, vibrational frequencies, atomic charges, dipole moment, rotational constants and several thermodynamic parameters in the ground state were calculated using ab initio HartreeFock (HF) and DFT (B3LYP) methods with 6-31++G (d, p) and 6-311++G (d, p) basis sets. With the help of different scaling factors, the observed vibrational wave numbers in FT-IR and FT-Raman spectra were analyzed and assigned to different normal modes of the molecule. Most of the modes have wave numbers in the expected range. The inductive effect of Chlorine atoms in the benzene molecule has also been investigated. 2011 Elsevier B.V. All rights reserved.

Article history: Received 1 February 2011 Received in revised form 23 March 2011 Accepted 4 April 2011 Keywords: 1,3-Dichlorobenzene Inductive effect Ab initio HartreeFock B3LYP FT-IR FT-Raman

1. Introduction Benzene is mainly used as an intermediate to make other chemicals. Its most widely-produced derivatives include styrene, which is used to make polymers and plastics, phenol for resins and adhesives, and cyclohexane, which is used in the manufacture of Nylon [1]. Benzene is a clear, colorless, no corrosive and highly ammable liquid with a sweet odor. It evaporates into the air very quickly and dissolves slightly in water [2]. Some industries use benzene to make plastics, resins, and Nylon and synthetic bers. Benzene is also used to make some types of rubbers, lubricants, dyes, detergents, drugs, and pesticides. Natural sources of benzene include volcanoes and forest res. Benzene is also a natural part of crude oil, gasoline, and cigarette smoke [3,4]. Chlorobenzene once was used for manufacturing of certain pesticides, most notably DDT by reaction with chloral (trichloroacetaldehyde), but this application has declined with the diminished use of DDT. At one time, chlorobenzene was the main precursor for the manufacture of phenol [5]. The major use of chlorobenzene is as an intermediate in the production of commodities such as herbicides, dyestuffs, and rubber. Chlorobenzene is also used as a high-boiling solvent in many industrial applications as well as in the laboratory [6]. Other applications include use as a ber

Corresponding author. Tel.: +91 9976306898; fax: +91 9976306898. E-mail address: mahadeva8452@yahoo.com (D. Mahadevan). 1386-1425/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.saa.2011.04.003

swelling agent and dye carrier in textile processing, as a tar and grease remover in cleaning and degreasing operations, as a solvent in surface coating and surface coating removers, and as a heat-transfer medium. Chlorobenzene is nitrated on a large scale to give a mixture of 2- and 4-nitrochlorobenzenes, which can be separated by fractional crystallization followed by distillation. 2-Nitrochlorobenzene is converted to related 2-nitrophenol, 2nitroanisole, bis(2-nitrophenyl)disulde, and 2-nitropaniline by nucleophilic displacement of the chloride with sodium hydroxide, sodium methoxide, sodium disulde and ammonia. The conversion of the 4-nitrochlorobenzene is similar [7]. Dichlorobenzene belong to the group of organic halogen compounds replacing two hydrogen atoms in benzene by chlorine atoms. 1,3-DCB used in the fumigant and insecticide, solvent, chemical intermediate to manufacture dyes, agrochemicals, pharmaceuticals and other organic synthesis (Fig. 1). In the present work, we have studied the FT-IR and FTRaman spectra of 1,3-DCB. The comparative IR and Raman spectra of experimental and calculated DFT (B3LYP) are given in Figs. 2 and 3 respectively. The ab initio HF and DFT calculations are performed to obtain the ground state optimized geometries and the vibrational wavenumbers of the different normal modes as well as to predict the corresponding intensities for the different modes of the molecule. In DFT methods, Beckes three parameter exact exchange-functional (B3) [8,9] combined with gradient-corrected correlational functional of Lee, Yang and Parr (LYP) [10,11] are the best predicting results for molecular

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Fig. 1. Molecular structure of 1,3-dichlorobenzene.

geometry and vibrational wave numbers for moderately larger molecule. 2. Experimental details The spectroscopic grade 1,3-DCB was purchased from Sigma Aldrich Chemicals, U.S.A. and used as such for recording spectra without further purication. The FT-IR spectrum of the title compound was recorded using Bruker IFS 66 V spectrometer in the range of 4000100 cm1 . The spectral resolution is 2 cm1 . The FT-Raman spectrum of 1,3-DCB was also recorded in the same instrument with FRA 106 Raman module equipped with Nd:YAG laser source operating at 1.064 m with 200 Mw power. Both the spectra were recorded in the range of 4000100 cm1 with scanning speed of 30 cm1 min1 of spectral width 2 cm1 . The frequencies of all sharp bands are accurate to 1 cm1 .

Fig. 3. (A) Experimental, (B) calculated, (C and D) FT-Raman spectra of 1,3dichlorobenzene.

3. Computational methods Many studies [1214] have shown that the DFT-B3LYP method in combination with the 6-31++G (d, p) and 6-311++G (d, p) basis sets are able to give the accurate energies, molecular structures, and infrared vibrational frequencies. The molecular structure of the 1,3DCB in the ground state is computed by performing both ab initio (HF) with 6-311++G (d, p) and DFT (B3LYP) with 6-31++G (d, p) and 6-311++G (d, p) basis sets. The optimized structural parameters are used in the vibrational frequency calculations at HF and DFT levels. The minimum energy of geometrical structure is obtained using level 6-311++G (d, p) basis sets. The calculated frequencies are scaled by 0.914, 0.87, 0.99 and 1.07 for HF/6-311++G (d, p) [15,16]. For B3LYP with 6-31++G (d, p) set is scaled 0.955, 0.93, 1.01, 0.99, and 1.07 and B3LYP/6-311++G (d, p) basis set is scaled with 0.96, 0.947, 1.01, 1.07 and 0.99 [17]. HF/DFT calculations for 1,3-DCB are performed using GAUSSIAN 03W program package on Pentium IV processor personal computer without any constraint on the geometry [18,19]. The comparative values of IR intensities and Raman activities are presented in Table 3 and their corresponding graph given in Figs. 4 and 5. 4. Results and discussion 4.1. Molecular geometry The molecular structure of the 1,3-DCB belongs to CS point group symmetry and its molecular structure is obtained from GAUSSAN 03 W and GAUSSVIEW programs are shown in Fig. 1. The molecule contains two Chlorine atoms with benzene ring. The comparative optimized structural parameters such as bond lengths, bond angles and dihedral angles are presented in Table 1. The comparative graphs of bond lengths, bond angles and dihedral angles of 1,3-DCB for three sets are presented in Figs. 68 respectively. From the theoretical values, it is found that most of the optimized bond lengths are slightly larger than the experimental values, due to that the theoretical calculations belong to isolated molecules in gaseous phase and the experimental results belong to molecules in solid state. Comparing bond angles and lengths of B3LYP with those of

Fig. 2. (A) Experimental, (B) calculated, (C and D) FTIR spectra of 1,3dichlorobenzene.

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Table 1 Optimized geometrical parameters for 1,3-dichlorobenzene computed at HF/6-311++ (d, p), B3LYP/6-31++G (d, p) and 6-311++G (d, p) basis sets. Geometrical parameters Methods HF/6-311++G (d, p) Bond length (A) C1C2 C1C6 C1Cl11 C2C3 C2H7 C3C4 C3Cl12 C4C5 C4H8 C5C6 C5H9 C6H10 Bond angle ( ) C2C1C6 C2C1Cl11 C6C1Cl11 C1C2C3 C1C2H7 C3C2H7 C2C3C4 C2C3Cl12 C4C3Cl12 C3C4C5 C3C4H8 C5C4H8 C4C5C6 C4C5H9 C6C5H9 C1C6C5 C1C6H10 C5C6H10 Dihedral angles ( ) C6C1C2C3 C6C1C2H7 Cl11C1C2C3 Cl11C1C2H7 C2C1C6C5 C2C1C6H10 Cl11C1C6C5 Cl11C1C6H10 C1C2C3C4 C1C2C3Cl12 H7C2C3C4 H7C2C3Cl12 C2C3C4C5 C2C3C4H8 Cl12C3C4C5 Cl12C3C4H8 C3C4C5C6 C3C4C5H9 H8C4C5C6 H8C4C5H9 C4C5C6C1 C4C5C6H10 H9C5C6C1 H9C5C6H10 1.382 1.381 1.741 1.382 1.071 1.381 1.741 1.384 1.072 1.384 1.074 1.072 121.5 118.9 119.4 118.3 120.8 120.8 121.5 118.9 119.4 118.8 120.2 120.9 120.8 119.5 119.5 118.8 120.2 120.9 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 B3LYP/6-31++G(d, p) 1.395 1.395 1.756 1.395 1.083 1.395 1.756 1.396 1.083 1.396 1.085 1.083 121.6 118.8 119.4 118.1 120.9 120.9 121.6 118.8 119.4 118.7 120.2 121.0 121.0 119.4 119.4 118.7 120.2 121.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 B3LYP/6-311++(d, p) 1.392 1.381 1.741 1.382 1.071 1.381 1.741 1.384 1.072 1.384 1.074 1.072 121.5 118.9 119.4 118.3 120.8 120.8 121.5 118.9 119.4 118.8 120.2 120.9 120.8 119.5 119.5 118.8 120.2 120.9 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 0.0 180.0 180.0 0.0 Experimental Values 1.744 1.090 1.744 1.090 1.090 1.090

HF, as a whole the formers are bigger than later and the B3LYP calculated values correlates well compared with the experimental data. Although the differences, calculated geometrical parameters represent a good approximation and they are the bases for the calculating other parameters, such as vibrational frequencies and thermodynamics properties. From the data shown in Table 1, it is seen that both HF and DFT (B3LYP/6-311++G (d, p)) levels of theory in general estimate same values of some bond lengths and bond angles. The perfect hexagonal structure of benzene is slightly distorted by the substitution of couple of Cl atoms and is evident by the order of CC bond length of the ring as C3C4 = C6C1 < C2C3 < C4C5 = C5C6 < C1C2. The calculated CCl bond lengths are found same at two positions

(C1Cl11 and C3Cl12) is 1.741 A (HF and DFT), 0.003 A differed from the experimental value 1.744 A [2022]. The breaking of benzene structure by Cl atoms also proved by the bond angle order as C1C2C3 < C3C4C5 = C1C6C5 < C4C5C6 < C2C3C4 < C2 C1C6. 4.2. Vibrational assignments The 1,3-DCB consists of 12 atoms, hence undergoes 30 normal modes of vibrations. Of the 30 normal modes of vibrations, 21 modes of vibrations are in plane and remaining 9 are out of plane. The bands that are in the plane of the molecule are represented as A and out-of-plane as A . Thus the 30 normal modes of vibrations

D. Mahadevan et al. / Spectrochimica Acta Part A 79 (2011) 962969 Table 2 Observed and HF/6-311++G (d, p), B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) level calculated vibrational frequencies of 1,3-dichlorobenzene. S.No. Symmetry species CS Observed frequency Calculated frequency (cm1 ) with HF/6-311++G (d, p) FT-Raman 3080s 1580w 1130w 1110w 1080w 1070w 1000vs 660m 400m 370w 210w 200w 180w Unscaled value 3381 3372 3367 3341 1762 1756 1619 1553 1420 1297 1227 1199 1174 1172 1103 1080 1020 998 879 851 759 724 607 486 464 429 398 224 212 184 Scaled value 3090 3082 3077 3053 1610 1527 1479 1419 1405 1387 1121 1095 1073 1071 1008 987 887 868 803 777 693 661 649 520 459 392 363 204 193 168 Calculated frequency (cm1 ) with B3LYP/6-31++G (d, p) Unscaled value 3237 3227 3223 3197 1621 1620 1495 1444 1342 1295 1190 1133 1101 1096 1009 985 904 882 785 784 679 673 544 444 430 397 369 202 197 167 Scaled value 3091 3081 3077 3053 1548 1506 1480 1458 1435 1385 1136 1121 1089 1085 998 940 863 842 777 776 672 666 582 475 460 393 365 199 195 178 Calculated frequency (cm1 ) with B3LYP/6-311++ G (d, p) Unscaled value 3219 3209 3205 3180 1611 1611 1490 1439 1328 1289 1188 1129 1097 1094 1011 982 903 883 786 783 695 674 548 444 430 397 369 201 197 166 Scaled value 3090 3080 3076 3011 1594 1525 1475 1453 1420 1379 1140 1117 1086 1083 1000 972 866 847 778 775 667 647 586 541 460 400 372 203 198 177 (CH) (CH) (CH) (CH) (C C) (C C) (C C) (CC) (CC) (CC) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CCl) (CCl) (CCC) (CCC) (CCC) (CCC) (CCC) (CCC) (CCl) (CCl) (CCl) (CCl) Vibrational assignments

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FTIR 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A 3090w 3070m 3010w 1580vs 1500w 1480s 1460vs 1410vs 1400s 1130vs 1110s 1080vs 1070vs 1000m 960w 860vs 840w 780vs 770vs 670vs 660w 640w 560w 480w

VS, very strong; S, strong; m, medium; w, weak; as, asymmetric; s, symmetric;

, stretching; , in plane bending; , out plane bending; , twisting.

of 1,3-DCB are distributed as Vib = 21A + 9A . In agreement with CS symmetry all the 30 fundamental vibrations are active in both Raman scattering and IR absorption. The harmonic-vibrational frequencies calculated for 1,3-DCB at HF and B3LYP levels using the triple split valence basis set along with the diffuse and polarization functions, 6-31++G (d, p) and 6-311++G (d, p) observed FT-IR and FT-Raman frequencies for various modes of vibrations have been presented in Table 2. Comparison of frequencies calculated at HF with the experimental values reveals the over estimation of the calculated vibrational modes due to the neglect of anharmonic-

ity in real system. Inclusion of electron correlation in the Density functional theory to certain extends makes the frequency values smaller in the comparison with the HF frequency data. Reduction in the computed harmonic vibrations, although basis set sensitive are only marginal as observed in the DFT values using 6-311++G (d, p). Any way not withstanding the level of calculations, it is customary to scale down the calculated harmonic frequencies in order to develop the agreement with the experiment.

Fig. 4. Comparative graph of IR intensities by HF and DFT (B3LYP).

Fig. 5. Comparative graph of Raman activities by HF and DFT (B3LYP).

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Table 3 Comparative values of IR intensities and Raman activities between HF/6-311++G (d, p), B3LYP/6-31++G (d, p) and B3LYP/6-311++ G (d, p) of 1,3-dichlorobenzene. S.No. Calculated with HF/6-311++G (d, p) IR intensity (Ai) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 0.084 0.441 0.000 0.519 3.502 4.388 4.699 0.000 2.315 22.807 89.611 49.811 17.513 0.000 2.950 0.210 16.247 13.487 15.597 26.861 0.112 2.372 16.304 70.187 28.724 90.110 5.576 1.089 3.044 0.474 Raman activity (I) 0.585 2.381 1.002 1.090 11.555 4.015 0.000 0.199 9.023 0.002 0.041 0.351 0.002 0.549 45.849 0.091 5.856 0.815 3.763 11.848 0.002 0.035 1.713 0.352 9.205 21.504 65.768 50.034 152.901 57.359 Calculated with B3LYP/6-31++G (d, p) IR intensity (Ai) 0.137 0.315 0.000 0.612 3.683 5.742 4.894 0.000 2.285 14.937 94.343 44.830 13.021 0.000 0.082 4.671 24.539 25.109 17.560 0.428 2.031 0.714 12.094 71.970 26.590 85.849 5.426 0.916 1.774 0.522 Raman activity (I) 0.774 2.829 1.211 1.018 10.128 3.324 0.000 0.152 6.916 0.005 0.073 0.078 0.015 0.257 0.061 43.494 12.702 0.068 15.738 1.327 0.282 1.651 2.345 0.001 9.012 21.836 88.391 60.323 171.154 68.733 Calculated with B3LYP/6-311++G (d, p) IR intensity (Ai) 0.092 0.284 0.000 0.676 3.745 5.917 4.163 0.000 2.254 17.313 95.836 43.449 15.457 0.000 0.159 3.998 25.161 25.537 17.884 0.476 1.727 1.350 12.692 75.789 85.876 28.054 4.741 0.499 1.313 0.764 Raman activity (I) 0.653 2.983 1.106 1.094 9.973 3.238 0.000 0.412 7.119 0.000 0.173 0.021 0.003 0.245 0.092 44.105 11.933 0.028 15.028 1.118 0.610 1.378 1.990 0.008 21.950 9.002 83.047 56.381 166.631 65.751

4.2.1. Computed IR intensity and Raman activity analysis Computed vibrational spectral IR intensities and Raman activities of the 1,3-DCB for corresponding wave numbers by HF method of 6-311++G (d, p) and DFT methods with B3LYP at 6-31++G(d, p) and 6-311++G (d, p) basis sets have been collected in Table 3. 1,3DCB is a non polar and belongs to CS point group. Comparison of IR intensity and Raman activity calculated by HF and DFT with B3LYP at 6-31++G (d, p) and 6-311++G (d, p) levels with experimental values exposes the variation of IR intensities and Raman activities. In the case of IR intensity, the values of HF are found to be higher than B3LYP at 6-311++G (d, p) levels whereas in the case of Raman

activity the effect is reversed. The similar effect was observed in the previous report [23]. 4.2.2. Computed vibrational frequency analysis The comparative graph of calculated vibrational frequencies by HF and DFT methods at HF/6-311++G (d, p), B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) basis sets for the 1,3-DCB are given in Fig. 9. From the gure, it is found that the calculated (unscaled) frequencies by B3LYP with 6-311++G (d, p) basis sets are closer to the experimental frequencies than HF method with 6-311++G (d, p) basis set. This observation is supported by the literature report [24]. The standard deviation (SD) calculation made between experimen-

Fig. 6. Bond length differences between theoretical (HF and DFT) approaches.

Fig. 7. Bond angle differences between theoretical (HF and DFT) approaches.

D. Mahadevan et al. / Spectrochimica Acta Part A 79 (2011) 962969 Table 4 Standard deviation of frequencies by HF 6-311++G (d, p), DFT (B3LYP) at 6-31++G (d, p) and 6-311++G (d, p) basis sets. S.No. 1 2 3 4 Basic set levels Experimental value HF/6-311++(d, p) B3LYP/6-31++(d, p) B3LYP/6-311++(d, p) Total values 35,050 38,058 35,672 35,558 Average 1168.33 1268.6 1189.06 1185.26 Standard Deviation 77.05 32.05 29.13

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Deviation ratio 2.40 2.64

culated frequencies by B3LYP/6-311++G (d, p) basis sets are closer to the experimental frequencies than HF method. 4.2.3. CH vibrations The aromatic structure shows the presence of CH stretching vibrations in the region 31003000 cm1 which is the characteristic region for ready identication of CH stretching vibrations [2528]. The bands appeared at 3090, 3080, 3070 and 3010 cm1 in the 1,3-DCB have been assigned to CH ring stretching vibrations. The CH in-plane ring bending vibrations are normally occurred as a number of strong to weak intensity bands in the region 13001000 cm1 [29]. In the present case, four CH in-plane bending vibrations of the present compound are identied at 1130, 1110, 1080, 1070 cm1 . The calculated frequencies of B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) methods for CH in-plane bending vibrations showed excellent agreement with recorded spectrum as well as literature data. The CH out-of-plane bending vibrations are normally observed in the region 1000809 cm1 [3035]. The four CH out-of-plane bending vibrations are observed at 1000, 960, 860 and 840 cm1 . These in-plane and out-of-plane vibrational frequencies are found to be well within their characteristic region.
Fig. 8. Dihedral angle differences between theoretical (HF and DFT) approaches.

tal and computed frequencies (HF/DFT) for the 1,3-DCB is presented in Table 4. According to the SD, the computed frequency deviation decrease in going from HF/6-311++G (d, p) to B3LYP/6-31++G (d, p) to B3LYP/6-311++G (d, p). The deviation ratio between HF/6311++G (d, p) and B3LYP/6-31++G (d, p) is 2.40 and HF/6-311++G (d, p) and B3LYP/6-311++G (d, p) is 2.64. It also proved that, the cal-

4.2.4. CC vibrations Generally C C stretching vibrations in aromatic compounds form a band in the region of 14301650 cm1 [36,37]. Accordingly, in the present study, the C C stretching vibrations of 1,3-DCB are observed at 1580, 1500 and 1480 cm1 . The theoretically computed frequencies for CH in-plane bending vibrations by B3LYP/6-311++G (d, p) method showed excellent agreement with recorded spectrum as well as literature data. Ring CC stretching vibrations normally occur in the region 15901430 cm1 [37]. In the present case, the CC stretching vibrations are found at 1460, 1410 and 1400 cm1 . When compared to the literature range cited above, there is a considerable decrease in frequencies which is also worsening with the increase of mass of substitutions. In the present work, three strong bands found at 670, 660 and 640 cm1 are assigned to CCC in-plane bending and three supplementary bands

Fig. 9. Comparative graph of computed frequencies (HF and DFT) with experimental frequencies.

Fig. 10. Variation of the atomic charges for different basis sets of HF and DFT.

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Table 5 Theoretically computed zero point vibrational energy (kcal mol1 ), rotational constants (GHz), rotational temperature (K), thermal energy (kcal mol1 ), molar capacity at constant volume (cal mol1 K1 ) entropies (cal mol1 K1 ) and dipole moment (Debye) for 1,3-dichlorobenzene. Parameters Zero point vibration energy Rotational constants HF/6-311++ (d, p) 54.429 2.856 0.864 0.663 0.137 0.041 0.031 0.889 0.889 56.578 58.355 2.981 2.981 17.157 23.119 40.845 28.285 11.330 80.461 1.938 B3LYP/6-31++ (d, p) 51.018 2.804 0.849 0.652 0.134 0.040 0.031 0.889 0.889 53.436 55.213 2.981 2.981 18.948 24.909 40.845 28.338 12.901 82.085 2.250 B3LYP/6-311++(d, p) 50.854 2.815 0.852 0.654 0.135 0.040 0.031 0.889 0.889 53.270 55.047 2.981 2.981 18.937 24.899 40.845 28.328 12.909 82.083 2.223

Rotational temperature Energy Translational Rotational Vibrational Total Molar capacity at constant volume Translational Rotational Vibrational Total Entropy Translational Rotational Vibrational Total Dipole moment

Table 6 Mulliken atomic charges of 1,3-dichlorobenzene performed at HF/6-311++G (d, p), B3LYP/6-31++G (d, p) and B3LYP/6-311++G (d, p) basis sets. Atoms Mulliken atomic charges HF/6-311++G (d, p) C1 C2 C3 C4 C5 C6 H7 H8 H9 H10 Cl11 Cl12 0.346 0.379 0.346 0.579 0.577 0.579 0.234 0.215 0.224 0.215 0.266 0.266 B3LYP/6-31++G (d, p) 0.251 0.645 0.251 0.375 0.003 0.375 0.123 0.138 0.136 0.138 0.179 0.179 B3LYP/6-311++G (d, p) 0.455 0.762 0.455 0.533 0.464 0.533 0.174 0.180 0.192 0.180 0.326 0.326

are assigning at 560, 480 and 400 cm1 to CCC out-of-plane bending. These assignments are in line with the assignments proposed by the literature [38,39]. 4.2.5. CCl vibrations The vibration belonging to the link between the CCl is signicant to discuss here since mixing of vibrations are possible due to the lowering of the molecular symmetry and the presence of heavy atoms on the periphery of the molecule [40]. The assignments of CCl stretching and deformational modes have been made through comparison with similar assignments in other halogens substituted benzene derivatives. The CCl stretching vibration gives generally a strong band in the region 750580 cm1 [41,42]. In this case, a strong band for CCl stretching vibration is observed at 780, 770 cm1 . CCl in plane bending vibration compounds form a band in the region of 385265 cm1 [43]. Accordingly, the bands are identied at 370, 210 cm1 have been assigned to CCl in-plane bending modes. The CCl out-of-plane bending vibrations have been established at 200, 180 cm1 . 4.2.6. Other molecular properties Several calculated thermodynamic parameters are presented in Table 5. Scale factors have been recommended [44] for an accurate prediction in determining the zero-point vibration energies (ZPVE), and the entropy, Svib (T). The variations in the ZPVEs seem

to be insignicant. The total energies are found to decrease with the increase of the basis set dimension. The changes in the total entropy of 1,3-DCB at room temperature at different basis set are only marginal. 4.2.7. Mulliken atomic charges The total atomic charges of 1,3-dichlorobenzene obtained by Mulliken population analysis with different (HF) with 6-311++G (d, p) and DFT (B3LYP) with 6-31++G (d, p) and 6-311++G (d, p) basis sets were listed in Table 6. The negative values on C2, C4, C5and C6 atom in the aromatic ring lead to a redistribution of electron density. Due to this strong negative charges, C1 and C3 accommodate higher positive charge and becomes more acidic. The atomic charge obtained from B3LYP/6-311++G (d, p) basis set shows that Chlorine atom is more acidic due to more positive charge. The better represented graphical form of the results has been done in Fig. 10. Fig. 10 shows Mulliken charge of atoms for (HF) with 6-311++G (d, p) and DFT (B3LYP) with 6-31++G (d, p) and 6-311++G (d, p) basis sets, respectively. 5. Conclusion Attempts have been made in the current paper for the proper frequency assignments for the compound 1,3-dichlorobenzene from the FT-IR and FT-Raman spectra. The equilibrium geometries,

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vibrational frequencies, infrared intensities and Raman activities are calculated and analyzed by HF and DFT(B3LYP) levels of theory utilizing 6-31++G (d, p) and 6-311++G (d, p) basis sets. Comparison between the calculated vibrational frequencies and the experimental values indicates that both the methods can predict the FT-IR and FT-Raman spectra of the title compound well. The Scaling factors used in this study made a reliable agreement between the calculated and experimental values. In particular, the results of DFT-B3LYP method indicate better t to experimental ones than ab initio HF upon evaluation of vibrational frequencies. The optimized geometrical parameters calculated at B3LYP basis sets are slightly larger than those calculated at HF level. The atomic charges and dipole moment in the title molecule are also discussed elaborately. Several thermodynamic parameters of the title molecule are comparatively discussed. References
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