Spectrochimica Acta Part A 75 (2010) 1523–1529 Contents lists available at ScienceDirect Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy journal homepage: www.elsevier.com/locate/saa FT-IR, FT-Raman, NMR spectra and DFT calculations on 4-chloro-N-methylaniline A. Usha Rani a,b , N. Sundaraganesan c,∗ , M. Kurt d , M. Cinar e , M. Karabacak e a Avvaiyar Government College for Women, Karaikal 609602, India b Research and Development Centre, Bharathiar University, Coimbatore 641046, India c Department of Physics (Engg.), Annamalai University, Annamalai Nagar, Chidambaram 608002, Tamil Nadu, India d Ahi Evran Üniversitesi Fen Edebiyat Fakültesi Fizik Bölümü, As ¸ ıkpas ¸ a Kampusü 40100, Kırs ¸ ehir, Turkey e Department of Physics, Afyonkarahisar Kocatepe University, 03040 Afyonkarahisar, Turkey article info Article history: Received 21 November 2009 Received in revised form 10 January 2010 Accepted 3 February 2010 Keywords: FT-IR FT-Raman 1 H NMR 13 C NMR TED 4-Chloro-N-methylaniline abstract In this work, the vibrational spectral analysis was carried out by using FT-IR and FT-Raman spectroscopy in the range 400–4000 and 50–3500 cm -1 respectively, for the title molecule. The structural and spectro- scopic data of the molecule in the ground state were calculated by using density functional method using 6-311++G(d,p) basis set. The vibrational frequencies were calculated and scaled values were compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete assignments of all the vibrational mode were performed on the basis of the total energy distributions (TED). 13 C and 1 H NMR chemical shifts results were given and are in agree- ment with the corresponding experimental values. The theoretically constructed FT-IR and FT-Raman spectra exactly coincides with experimental one. © 2010 Elsevier B.V. All rights reserved. 1. Introduction Aromatic amines, more generally anilines have been widely used as chemical dye industries, nano-cable manufacturing in electronic industries, coating by electro-polymerization in steel industries pharmaceuticals’ manufacturing and other industrial purposes [1–5]. Moreover, some derivatives of aniline are used as local anesthetics in medicine. As a result, understanding of physical properties of aniline and its derivatives is crucial. The large numbers of experimental [6–8] and theoretical investigations have focused on elucidating the structure and normal vibrations of aniline and its methyl derivatives [1–3,9–11]. The structure of aniline was reported theoretically using semi-empirical [12,13] and ab initio methods [12–15]. Vibrational analysis based on FT-IR in vapour, solution and liquid phases and Raman spectra in liq- uid state have been reported for aniline [16]. It was also studied in the gas phase from microwave spectroscopy [1,17] and in the solid state from X-ray crystallography [18]. Reuben investigated the isotopic multiplets in the 13 C NMR spectra of aniline derivatives and nucleosides with partially deuterated amino groups based on effect of intra- and intermolecular hydrogen bonding [19]. Many studies [1,9,20–22] were performed recently to assign complete vibrational mode and frequency analysis. Altun et al. also stud- ∗ Corresponding author. Tel.: +91 413 2281354. E-mail address: sundaraganesan n2003@yahoo.co.in (N. Sundaraganesan). ied vibrational modes and frequency analysis of m-methylaniline [1]. Some band observations of p-methylaniline in the IR spectrum are given in the literature [6,23–26]. The vibrational spectrum of chloromethyl aniline [25] and fluoromethyl aniline [27,28] is given in the literature. Shanker et al. studied 2-chloro-6-methylaniline using polarized Raman and IR spectra [29]. Barluenga et al. synthe- sized 2-chloro-N-methylaniline and studied its 1 H and 13 C NMR spectra [30]. The low temperatures 13 C NMR spectra allowed the determination of the rotational barrier of N-methyl aniline in solu- tion was reported by Lunazzi et al. [31]. Barr et al. published a study on 1 H, 13 C, 15 N, 19 F, 29 Si NMR chemical shifts and coupling constants for nine N-substituted anilines [32]. Jet-cooled Fourier- transform microwave spectrum of N-methylaniline was recorded in the region of 10–26 GHz. It is analyzed to determine rotational constants and nuclear quadruple coupling constants by Fujitake et al. [8]. They gave a brief and detailed explanation of spectral analysis. Stein et al. reported that the two-dimensional solid state NMR studies of poly(aniline) [33]. Recently we reported an exper- imental and theoretical study on 1 H, 13 C and DEPT NMR spectra of N1-methyl-2-chloroaniline and 2-chloro-6-methylaniline along with IR, Raman and UV spectra [34,35]. Till now a detailed analysis of vibrational frequencies, IR and Raman spectra of 4-chloro-N-methylaniline (4-ClNMA) has not been reported. As a result we set out experimental and theoretical investigation of the vibrational and NMR spectra of this molecule. The density functional theory (B3LYP) calculations have been per- formed. We worked a detailed interpretation of the vibrational 1386-1425/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.saa.2010.02.010