A computational DFT study of third order nonlinear optical properties of organic 4-chloroaniline (CA) crystal C. Andal a,b,⇑ , V. Bharathi Devi a,b , P. Murugakoothan b a Dr M G R Educational and Research Institute, Chennai 600095, India b Pachaiyappa’s College, Chennai 600030, India article info Article history: Received 30 January 2020 Accepted 26 February 2020 Available online xxxx Keywords: Solution method Single crystal XRD UV–vis-NIR DFT abstract The organic 4-Chloroaniline (CA) crystal was developed using slow evaporation solution method with ethanol solvent at room temperature. The single crystal XRD study is useful to confirm the crystal struc- ture of the grown CA crystal. The linear optical properties of the grown CA crystal were calculated using UV–vis-NIR transmission spectrum study. The theoretical investigation of nonlinear optical property of the grown CA crystal was observed using the functional basic sets of B3LYP/6-31G (d, p) with the deter- mination of its second order hyperpolarizability and also its optical behavior from HOMO-LUMO analyze. The theoretical values of second order hyperpolarizability and energy band gap are compared experimen- tally with Z-scan technique study and UV–vis-NIR transmission spectrum analyze. Ó 2020 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Confer- ence on Nanotechnology: Ideas, Innovation and Industries. 1. Introduction In recent years, the growth of organic non-linear optical (NLO) materials is right significant process because of its wide applica- tions in the field of frequency shifting, optical modulation, optical switching, optical logic, and optical memory for the emerging tech- nologies in areas such as telecommunications, signal processing, and optical interconnections [1–3]. The organic materials are mainly chosen for the NLO applications because of its flexibility in the variation of its crystal structure, high nonlinearities and energy band gap values. In recent times, materials that preserve third order optical nonlinearities (v (3) ) are used extensively for optical switching device applications [4]. The organic material 4- Chloroaniline (CA) is an aromatic amine compound in which the –NH 3 group is attached directly to a carbon of the benzene ring. The CA material exhibits the delocalization property of non- bonded electron on N atom into the p system of the aromatic ring [5] and resulting third order nonlinearity. In this present work, the third order nonlinear optical properties of the grown CA crystal is stated theoretically using Density Functional Theory (DFT) with B3LYP functional using 6-31G(d, p) basis set with the help of Gaus- sian 09W package and also experimentally using Z-scan technique. 2. Experimental methods The 4-chloroaniline (CA) crystals of high purity (AR grade) were grown from ethanol solution at room temperature using slow evaporation solution method. The saturated solutions of the respective materials were prepared, filtered and crystallization was allowed to take place in a period of 7 days. The picture of the as grown crystals of CA is shown in Fig. 1. 3. Results and discussion 3.1. Single crystal X-ray diffraction analysis The determination of crystal structure of any grown crystal is done using single crystal X-ray diffraction study. The grown CA crystal was exposed to single crystal X-ray diffraction studies using a Bruker AXS diffractometer with MoKa radiation (k = 0.7107 Å). The grown CA crystal belongs to orthorhombic structure with cen- trosymmetric space group of P nma and cell parameters values as a = 8.665 Å, b = 7.397 Å, c = 9.281 Å, a = b = c = 90°, V = 594.93 Å 3 and Z-4 which are in good agreement with the reported values [6]. https://doi.org/10.1016/j.matpr.2020.02.897 2214-7853/Ó 2020 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Conference on Nanotechnology: Ideas, Innovation and Industries. ⇑ Corresponding author at: Dr M G R Educational and Research Institute, Chennai 600095, India. E-mail address: andal.phy@drmgrdu.ac.in (C. Andal). Materials Today: Proceedings xxx (xxxx) xxx Contents lists available at ScienceDirect Materials Today: Proceedings journal homepage: www.elsevier.com/locate/matpr Please cite this article as: C. Andal, V. Bharathi Devi and P. Murugakoothan, A computational DFT study of third order nonlinear optical properties of organic 4-chloroaniline (CA) crystal, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.02.897