Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255

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Spectrochimica Acta Part A: Molecular andBiomolecular Spectroscopy

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Vibrational analysis of 4-chloro-3-nitrobenzonitrile by quantumchemical calculations

Yusuf Sert a,⇑, Çagrı Çırak b, Fatih Ucun c

a Department of Physics, Faculty of Art & Sciences, Bozok University, Yozgat, Turkeyb Department of Physics, Faculty of Art & Sciences, Erzincan University, Erzincan, Turkeyc Department of Physics, Faculty of Art & Sciences, Süleyman Demirel University, Isparta, Turkey

h i g h l i g h t s

" The FT-IR and l-Raman spectra of 4-chloro-3-nitrobenzonitrile arerecorded in solid phase.

" Theoretical harmonic andanharmonic vibrational frequenciesand optimized molecular structureare given for the first time.

" The complete assignments areperformed on the basis of the totalenergy distribution (PED).

" The HOMO and LUMO energies havebeen calculated.

1386-1425/$ - see front matter � 2013 Elsevier B.V. Ahttp://dx.doi.org/10.1016/j.saa.2013.01.046

⇑ Corresponding author. Tel.: +90 354 2421021; faxE-mail address: yusufsert1984@gmail.com (Y. Sert

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o

Article history:Received 2 November 2012Received in revised form 11 January 2013Accepted 17 January 2013Available online 31 January 2013

Keywords:4-Chloro-3-nitrobenzonitrileFT-IR spectral-Raman spectraHFDFT

a b s t r a c t

In the present study, the experimental and theoretical harmonic and anharmonic vibrational frequenciesof 4-chloro-3-nitrobenzonitrile were investigated. The experimental FT-IR (400–4000 cm�1) and l-Raman spectra (100–4000 cm�1) of the molecule in the solid phase were recorded. Theoretical vibrationalfrequencies and geometric parameters (bond lengths and bond angles) were calculated using ab initioHartree Fock (HF), density functional B3LYP and M06-2X methods with 6-311++G(d,p) basis set by Gauss-ian 09 W program, for the first time. The assignments of the vibrational frequencies were performed bypotential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geomet-ric parameters and vibrational frequencies were compared with the corresponding experimental data,and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbi-tal (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

� 2013 Elsevier B.V. All rights reserved.

Introduction

Benzonitrile is phenyl cyanide compound derived mainly frombenzoic acid reaction with lead thiocyanate by heating. It is colorlessliquid with a boiling point of 197 �C and having a smell of bitter al-monds. Benzonitrile is used as a solvent and chemical intermediatefor the synthesis of pharmaceuticals, dye stuffs and rubber chemi-cals through the reaction of alkylation, condensation, esterification

ll rights reserved.

: +90 354 2421022.).

hydrolysis, halogenation or nitration. Many derivatives of benzoni-trile are widely used in industry and medicinal fields. The mainproduct of benzonitrile-benzoic acid is used in medicine as urinaryantiseptic in the form of salt and in vapor form for disinfecting bron-chial tubes. Extensive literature survey conducted reveals that agood amount of work has been done on benzonitrile and its deriva-tives because of their interesting biochemical and physical proper-ties [1–27]. To our best knowledge, no computational vibrationalstudy on 4-chloro-3-nitrobenzonitrile was published in the litera-ture. Hence of these, in this work, the theoretical and experimentalstudies were performed to give a detailed description of the

Table 1Experimental and calculated optimized structure parameters of 4-chloro 3-

Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255 249

molecular structure and vibrational harmonic and anharmonicspectra of 4-chloro-3-nitrobenzonitrile.

nitrobenzonitrile.

Parameters Experimentala Calculated 6-311++G(d,p)

B3LYP M06-2X HF

Bond lengths (Å)C1AC2 1.407 1.386 1.384 1.379C1AC6 1.386 1.403 1.397 1.389C2AC3 1.316 1.396 1.393 1.387C3AC4 1.406 1.399 1.394 1.387C3ACl1 1.726 1.736 1.722 1.724C4AC5 1.370 1.388 1.385 1.380C4AN11 1.466 1.481 1.478 1.466C5AC6 1.354 1.396 1.391 1.383C6AC7 1.434 1.431 1.436 1.442N1AO2 1.214 1.223 1.211 1.187

Experimental details

4-Chloro-3-nitrobenzonitrile (4C3NB) was purchased at Sigma–Aldrich Cooperation to record its spectra and, used with no furtherpurification. FT-IR spectrum (400–4000 cm�1) of the molecule inpotassium bromide (KBr) disk was recorded by Thermo Scientific,Nicolet 6700 FTIR Spectrometer with a resolution of 4 cm�1 atroom temperature. Its l-Raman spectrum (100–4000 cm�1) wasrecorded by Jasco NRS-3100 Laser Raman Spectrophotometer atroom temperature. The 785 nm line of green diode laser was usedas the exciting light, and 25 scans were accumulated.

N1AO1 1.213 1.219 1.207 1.182C7AN2 1.166 1.155 1.150 1.130R2 0.9676 0.9665 0.9637

Bond angles (�)C2AC1AC6 121.3 120.2 120.0 120.1C1AC2AC3 121.3 120.7 120.6 120.6C2AC3AC4 117.8 118.6 118.5 118.6C2AC3ACl1 118.9 118.4 118.4 118.1C4AC3ACl1 121.5 123.0 123.1 123.2C3AC4AC5 122.2 121.2 121.6 121.4C3AC4AN1 121.1 122.5 122.2 122.5C5AC4AN1 116.6 116.3 116.2 116.1C4AC5AC6 117.8 119.7 119.2 119.4C1AC6AC5 119.5 119.5 119.9 119.9C1AC6AC7 120.3 120.3 120.0 120.2C5AC6AC7 118.8 120.1 119.9 120.0C4AN1AO2 117.9 116.5 116.4 116.4C4AN1AO1 117.9 117.6 117.5 117.7O2AN1AO1 124.2 125.9 126.1 125.8R2 0.8099 0.8373 0.8176

a [27].

Computational details

The initial atomic coordinates for geometry optimization wastaken from Gauss View software database [28]. The molecularstructure of 4C3NB in the ground state (in gas phase) was opti-mized by DFT/B3LYP, M06-2X and HF and methods with 6-311++G(d,p) basis set level, and the optimized structure was usedin the vibrational frequency calculations. The calculated harmonicand anharmonic vibrational frequencies were scaled by 0.9051(HF) and 0.9614 (B3LYP) for 6-311++G(d,p) level [28]. Additionally,the calculated harmonic vibrational frequencies were scaled by0.9489 (M06-2X) for 6-311++G(d,p) level [29]. The moleculargeometry was not restricted, and all the calculations (vibrationalwavenumbers, geometric parameters and other molecular proper-ties) were performed by using Gauss View molecular visualizationprogram [30] and Gaussian 09 W program package on a computingsystem [31]. Additionally, the calculated vibrational frequenciesare clarified by means of the potential energy distribution (PED)analysis of all the fundamental vibration modes by using VEDA 4program [32]. VEDA 4 program has been used in previous studiesby many researchers [33–35]. All the vibrational assignments havebeen made at B3LYP/6-311++G(d,p) level. Therefore, some assign-ments may correspond to its previous or next vibrational fre-quency value at M06-2X and HF/6-311++G(d,p) level.

Fig. 1. The optimized molecular structure of the 4C3NB.

Results and discussion

Geometric structure

Chemical formula of 4-chloro-3-nitrobenzonitril (4C3NB) is C7-

H3ClN2O2. From the single crystal X-ray analysis data of 4C3NB itis observed that its crystal possesses space P�1 and belongs to tri-clinic system with the following cell dimensions: a = 7.2260 Å,b = 7.7610 Å, c = 7.7970 Å and a = 110.27�, b = 91.86� andc = 107.22� and V = 387.22 Å3 [27]. The measured density of themolecule is 1.565 mg/m3. The theoretical and experimental struc-ture parameters (bond lengths and angles) of the molecule are tab-ulated in Table 1, in accordance with the atom numbering schemegiven in Fig. 1. The monatomic substituents of benzonitrilies haveC2V symmetry [26] whereas 4-chloro-3-nitrobenzonitrile has C1

symmetry. From the theoretical geometry we have found that mostof the optimized bond lengths are slightly longer or shorter thanthe experimental values at the DFT/B3LYP, M06-2X and HF levels,due to the fact that the theoretical calculations belong to isolatedmolecule in gaseous phase while the experimental results belongto one in solid state. In addition, the comparation of the theoreticalbond lengths and bond angles at the B3LYP, M06-2X and HF levelsas a whole shows that the calculated values at B3LYP level corre-late well with the experimental ones.

The CACl bond length is calculated as 1.736 Å (B3LYP) and1.724 Å (HF) for 6-311++G(d,p) level. This bond length was exper-imentally found 1.726 Å by Liu et al. [27]. The crystals suitable forX-ray analysis were obtained by slow evaporation of a methanolsolution. Akyüz et al. [36] have calculated this bond length as1.746 Å for 3-chloropyridine, and it was calculated as 1.748 Å for2-chloropyridine by using force field calculations [37]. This bondlength was also observed as 1.739 Å for similar molecules [38].The experimental value of the C14AN15 bond length is 1.166 Å[27]. For it we have found the almost closest value as 1.155 Å atthe B3LYP level, but as 1.130 Å at the HF level. This bond lengthwas calculated as 1.137 Å for a similar structure [38]. The bond

250 Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255

angles calculated using the HF and B3LYP methods show the sametrend as variation in bond lengths. To compare our all the calcu-lated values with the experimental data we have obtained the lin-ear correlation coefficients (R2) with linear regression analysis ofthe theoretical and experimental bond lengths and bond angles.These coefficients can be seen in the last line of Table 1. From thesevalues it can easily be said that the geometric parameters calcu-lated with the B3LYP method are much closer to the experimentalresults. As seen from Table 1, CAH bonds and CACAH angles wereexcluding due to H atoms were positioned geometrically, withCAH = 0.93 Å for aromatic H in the single crystal X-ray study [27].

The largest differences between the calculated and experimen-tal geometries are 0.153 Å (B3LYP) compared with 0.144 Å (HF)and 0.077 Å (M06-2X) for the bond lengths and 2.5� (B3LYP) com-pared with 2.8� (HF) and 1.9� (M06-2X) for the bond angles.

Additionally, to determine the exact orientation of NO2 group,we have scanned the total energy for the C3AC4AN1AO2 dihedralangle from h = 0� to h = 180� in interval 1� by using B3LYP methodwith 6-311++G(d,p) basis set level (Fig. 2). As clearly seen from thecurve in the figure, the 4C3NB molecule has the lowest energywhen C3AC4AN1AO2 dihedral angle are 44� (ground state) and138�, respectively.

Vibrational analysis

The experimental FT-IR and l-Raman spectra of the moleculeare shown in (Figs. 3 and 4) respectively. For comparative purposethe calculated IR and Raman spectra are shown in Fig. 5. The scaledcalculated harmonic and anharmonic vibrational frequencies at HFand B3LYP levels, observed vibrational frequencies, and detailedPED assignments are tabulated in Table 2. Also, harmonic frequen-cies are calculated for gaseous phase of isolated 4C3NB, whileexperimental spectra are obtained from solid phase of 4C3NB.4C3NB molecules are interconnected by intermolecular CAH� � �Oand CAH� � �N weak hydrogen bonds in solid phase [27]. So, thereis disagreement between the observed and the calculated frequen-cies in some modes. To our knowledge, there are no theoreticalstudies on vibrational assignment of 4C3NB in the literature. So,

Fig. 2. Energy curve as a function of th

in order to introduce detailed vibrational assignments of 4C3NB,we have done the PED analysis of the molecule. All the calculatedmodes are numbered from the largest to the smallest frequencywithin each fundamental wavenumber.

CAH vibrationsThe substituted benzenes give rise to CAH stretching, CAH in-

plane bending, and CAH out of plane deformations. The hetero aro-matic structure shows the presence of CAH stretching vibrations inthe region 3000–3100 cm�1 which is the characteristic region forthe ready identification of such CAH stretching vibrations [39–41]. Accordingly, in this study, the CAH vibrations of the title com-pound are observed at 3098, 3070, 3047 cm�1 in FTIR and 3111,3072, 3049 cm�1 in the FT-Raman spectrum. These modes are fur-ther supported by the PED contribution of almost %100. The CAHin-plane and out-of-plane bending modes of the compound showconsistent agreement with the computed B3LYP results, and arelisted in Table 2.

CACl vibrationsThe vibrational mode belonging to the bond between the ring

and halogen atom is worth to discuss here, since mixing of vibra-tions is possible due to the lowering of the molecular symmetryand the presence of heavy atom on the periphery of the molecule[42]. The assignments of CACl stretching and deformation vibra-tion modes have been made by comparison with halogen substi-tuted benzene derivatives [43]. Mooney [44,45] have assignedthe vibrations of the CAX group (X = Cl, Br, I) in the frequencyrange of 1129–480 cm�1. The CACl stretching mode appeared asa mixed mode. It has also been observed that in benzene deriva-tives containing a Cl atom, the CACl stretching frequency appearsin 600–800 cm�1 region [46]. Based on the above literature data,the theoretically computed vibrationals at 629/626/644 cm�1 and569/570/583 cm�1 (v25, v26), respectively, by using B3LYP/M06-2X/HF 6-311++G(d,p) method are assigned to the CACl stretchingvibration, and show good agreement with the experimental FT-IR/FT-R bands at 640/641 and 585/585 cm�1.

e C3AC4AN1AO2 dihedral angle.

Fig. 3. The experimental FT-IR spectrum of the title molecule in solid phase.

Fig. 4. The experimental l-Raman spectrum of the title molecule in solid phase.

Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255 251

C„N vibrationsUnsaturated or aromatic nitriles, in which the double bond or

ring is adjacent to the C„N group, absorbs more strongly in theinfrared than saturated compounds, and the related band occursat somewhat lower frequency near 2230 cm�1 [47]. In our presentwork, theoretically computed values (v4) is assigned to the stretch-ing of C„N group, and it is in a good agreement with our experi-mental spectrum; the observed band in FT-R spectrum at

2238 cm�1. The vibrational mode (v4), which is calculated at2345 cm�1 by HF, at 2250 cm�1 by B3LYP and at 2292 cm�1 byM06-2X is assigned to the in-plane stretching vibration of C„Ngroup.

NO2 vibrationsThe characteristic group frequencies of the nitro group are rel-

atively independent of the rest of the molecule which make this

Fig. 5. Comparative graph of calculated IR and Raman spectra with 6-311++G(d,p) basis set.

252 Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255

group convenient for identification. Aromatic nitro compoundshave strong absorption due to the asymmetric and symmetricstretching vibrations of NO2 group in the range 1570–1485 cm�1

and 1370–1320 cm�1, respectively [48]. Randle and Whiffen [49]have assigned the symmetric stretching frequency to a band lyingbetween 1333 and 1370 cm�1 and asymmetric stretching fre-quency between 1494 and 1539 cm�1 in the spectra of nitroben-zenzene derivatives. Rastogi et al. [26] have assigned the bands

at 1350 and 1349 cm�1 in IR and at 1340 cm�1 in the Raman tosymmetric stretching vibration of NO2 group while assigned thebands appear at 1550, 1549 and 1552 cm�1 in IR and 1550 cm�1

in Raman to its asymmetric stretching vibration. In the presentinvestigation values of asymmetric and symmetric modes of NO2

group were computed 1579 cm�1 and 1545 cm�1, respectively(by B3LYP method) in agreement with the experimentally recordedvalues at 1604 cm�1 and 1560 cm�1. The bands at 793, 640 and

Table 2Vibrational assignment for 4-chloro-3-nitrobenzonitrile.

Vib. No Assignmentsa Experimental freq.(cm�1)

Calculated freq. (cm�1)B3LYP6-311++G(d,p)

Calculated freq. (cm�1)M06-2X6-311++G(d,p)

Calculated freq. (cm�1)HF6-311++G(d,p)

IR R Har. Anha. Har. Anhar Har. Anhar.

m1 tCH(96)sym. 3098 3111 3093 3094 3072 3082 3064 3266m2 tCH(97)sym. 3070 3072 3088 3084 3062 3324 3057 3258m3 tCH(93)asym. 3047 3049 3076 3044 3034 3802 3041 3239m4 tC„N(89)+tCC(11) 2238 2239 2250 2308 2292 2362 2345 2570m5 tCC(43)+dHCC(15)+tNO(12) 1604 1605 1579 1605 1633 1690 1657 1791m6 tNO(75) 1560 1560 1545 1572 1591 1644 1617 1742m7 tCC(45)+dCCC(26) 1541 1540 1522 1545 1549 1600 1576 1704m8 dHCC(42)+tCC(15) 1475 1476 1445 1473 1450 1509 1491 1611m9 tCC(46)+dHCC(19) 1403 1404 1367 1397 1397 1439 1480 1603m10 tNO(79)+dONO(12) 1368 1369 1330 1357 1371 1440 1389 1509m11 tCC(82) 1270 1273 1264 1288 1249 1287 1263 1375m12 dHCC(53)+tCC(12) 1270 1273 1239 1270 1226 1292 1199 1305m13 tCC(38)+dHCC(21)+dCCC(11) 1203 1206 1178 1202 1177 1221 1153 1259m14 dHCC(54)+tCC(11) 1151 1152 1127 1159 1117 1220 1133 1232m15 dHCC(35)+tCC(30)+tCCl(11)+tCN(10) 1140 1142 1101 1125 1107 1144 1091 1193m16 dCCC(50)+tCCl(12) 1053 1053 1024 1047 1025 1067 1049 1141m17 sHCCC(75)+sCCCC(15) 984 952 969 947 1052 999 1084m18 tCN(12)+sHCCC(11)+dONO(10) 916 917 895 917 904 938 947 1025m19 sHCCC(37)+sCCCC(15) 916 917 892 913 900 829 926 1010m20 sCCCC(86) 844 854 816 837 813 899 855 930m21 dONO(47) 793 797 779 801 787 821 811 882m22 cOCON(57)+cNCCC(14) 751 755 748 759 757 779 795 863m23 sCCCC(29) 691 712 694 692 691 698 722 757m24 dCCC(51) 671 674 663 678 659 689 675 736m25 cCCCC(14)+dONC(11)+tCCl(10) 640 641 629 645 626 663 644 703m26 tCCl(24)+tCC(12) 585 585 569 580 570 593 583 630m27 dNCC(29)+dCCC(28) 554 556 554 568 553 577 569 622m28 dONC(25)+sNCCC(11)+dNCC(10) 508 511 497 505 499 502 516 558m29 sNCCC(28)+cClCCC(28)+sCCCC(17) 440 442 434 443 433 445 453 490m30 sCCCC(37)+tCN(13)+dClCC(12) 406 410 401 409 401 415 414 449m31 tCN(20)+sCCCC(18)+dONC(12) 381 370 378 371 391 380 413m32 dCCC(26)+tCCl(20)+dONC(11)+dCCC(10) 350 336 344 334 354 342 374m33 dClCC(32)+dNCC(25)+dCCC(12) 298 293 303 298 316 301 331m34 cClCCC(30)+sNCCC(20)+cCCCC(20)+cNCCC(12) 243 232 238 233 235 242 265m35 dNCC(40)+dClCC(29) 196 186 191 201 207 192 209m36 cNCCC(46)+sCCCC(14)+cCCCC(13) 148 129 131 128 145 136 147m37 dNCC(44)+dCCCl(43) 117 123 126 122 1271 127 138m38 sCCCC(46)+cCCCC(17)+cClCCC(14) 81 82 82 67 86 92m39 sONCC(90) 47 46 51 72 50 51R2 0.9996 0.9997 0.9992 0.9824 0.9976 0.9968

m, Stretching; d, bending; c, out of plane bending; s, torsion.a Potential energy distribution (PED), less than 10% are not shown.

Table 3Sum of electronic and zero point energies (hartree/particle), dipol moments (debye), Homo (a.u), Lumo (a.u) and Homo–Lumo gap values of 4-chloro-3-nitrobenzonitrile.

Methods 6-311++G(d,p)

Energies Dipole moment Homo energies Lumo energies Homo–Lumo gap value energies

B3LYP �988.74434669 4.0126 �0.29903 �0.12380 �0.17523M06-2X �988.5094983 4.0384 �0.34831 �0.07996 �0.26835HF �984.93952471 4.2745 �0.38839 0.02542 �0.41381

Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255 253

508 cm�1 in IR spectrum and 797, 641 511 and 381 cm�1 in Ramanspectrum have been assigned to NO2 deformation, rocking, waggingand torsional vibrational modes, respectively. The bending vibra-tions of NO2 group (scissoring, rocking, wagging and twisting) havecontributed to several normal modes in the low frequency region.

CAC vibrationsCAC stretchings of the ring carbon atoms are prominent. This is

reflected by their high relative intensities as presented in Table 2.In general, the bands around 1400–1650 cm�1 in benzene deriva-tives are assigned to skeletal stretching CAC bands [50]. The CACstretching vibrations were calculated to be 1579, 1522, 1445,1367, 1264, 1239, 1178, 1127, 1101 cm�1 at B3LYP/6-311++G(d,p)

level, 1633, 1549, 1450, 1397, 1249, 1226, 1177, 1117, 1107 cm�1

at M06-2X/6-311++G(d,p) and 1657, 1576, 1491, 1480, 1263,1198, 1153, 1133, 1091 cm�1 at the HF/6-311++G(d,p) level. Theo-retical results calculated at B3LYP, M06-2X and HF methods are ingood agreement with each other. Theoretically calculated CACACout of plane and CACAC in plane bending modes are seen in theTable 2.

Energies, dipole moments and molecular orbital energies

The sum of electronic and zero point energies, the dipole mo-ments, HOMO and LUMO and HOMO–LUMO gap energy values ofthe molecule at HF and B3LYP/6-311++G(d,p) level are given in

Fig. 6. Calculated HOMO–LUMO plots of 4C3NB.

254 Y. Sert et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 107 (2013) 248–255

Table 3. According to the theoretical results the molecule is moststable at B3LYP/6-311++G(d,p) level. The prediction of accurate di-pole moments is very important issue because the magnitude ofdipole moment is strongly related to structural stability. If thestructural stability is high, dipole moment is lower. For our mole-cule the structural stability at B3LYP/6-311++G(d,p) level is highsince the dipole moment is more lower than one at HF.

The highest occupied molecular orbital (HOMO) energies, thelowest unoccupied molecular orbital (LUMO) energies, and the gapenergy value of HOMO–LUMO for 4-chloro-3-nitrobenzonitrilewere calculated at HF and B3LYP/6-311++G(d,p) level of theory,and are shown in Table 3. As a result, at HF/6-311++G(d,p) level,HOMO–LUMO gap value is more higher than at B3LYP/6-311++G(d,p) level. The LUMO as an electron acceptor representsthe ability to obtain an electron and HOMO represents the abilityto donate an electron. 4-chloro-3-nitrobenzonitrile is interestingmodel compound. It is substituted by three substituents of differentelectron-donor–acceptor properties. The NO2 group is strong sigmaand pi electron acceptor, the CN group is also sigma and pi electronacceptor but weaker than the nitro group, while Cl is sigma electronacceptor but pi-electron donor [51]. Moreover, the NO2 and Cl sub-stituents are neighboring and the nitro group is strongly skewedfrom the ring plane as a result of intramolecular repulsion [27]. Be-cause, fact that the vibrational spectra of crystalline sample can beinterpreted by simulation of spectra of single molecule is a conse-quence of properly chosen substituents and relatively small inter-molecular interactions between molecules in crystals which arelimited to CAH� � �O and CAH� � �N interactions [27].

HOMO–LUMO plot at B3LYP/6-311++G(d,p) level is given inFig. 6. As seen from the figure, the HOMO is located on benzene, ni-trile and Cl atom, especially over the ring, the LUMO is more focusedon the nitro group but there is less concentration on nitrile group.

Conclusion

In this study, firstly, for the vibrational analysis of 4-chloro-3-nitrobenzonitrile we have taken the experimental IR and R spectra.

And then, we have calculated the geometric parameters, vibra-tional harmonic and anharmonic frequencies, PED assignmentsand the molecular orbital energies by using DFT/B3LYP, M06-2Xand HF methods with 6-311++G(d,p) basis set. Although the resultsof HF method in evaluating the vibrational harmonic frequencieshave shown better fit to the experimental data, B3LYP methodseems to be more appropriate in calculating the geometricalparameters. Our detailed PED% analysis of the molecule showeda good agreement with the experimental data. The HOMO andLUMO and gap energies of the molecule were also given.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, inthe online version, at http://dx.doi.org/10.1016/j.saa.2013.01.046.

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