Structural Properties and Nonlinear Optical Responses of Halogenated Compounds: A DFT Investigation on Molecular Modelling

Computational chemistry is used to evaluate structures of different compounds by using principles of theoretical and quantum chemistry integrated into useful computer programs. It is used to determine energies, dipole moments and thermodynamic properties of different compounds. The present work reports the computational study of six donor-acceptor dyes. The computational method CAM-B3LYP with 6-31G(d,p) was used in this research to determine the effect of halogens on non-linear optical compounds. HOMO-LUMO energy gaps, dipole polarizabilities, first hyperpolarizabilities, and absorption spectra of six studied compounds (dye 1: 4-(2-(4-fluorophenyl)ethynyl)benzenamine; dye 2: 4-(2-(4-chlorophenyl)ethynyl)benzenamine; dye 3: 4-(2-(4-bromophenyl)ethynyl)benzenamine; dye 4: 5-(2-(4-fluorophenyl)ethynyl)benzene-1,2,3-triamine; dye 5: 5-(2-(4-chlorophenyl)ethynyl)benzene-1,2,3-triamine; dye 6: 5-(2-(4-bromophenyl)ethynyl)benzene-1,2,3-triamine) with aniline and halo phenyl segments were computed by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Results indicate that all dyes showed wavelengths of maximum absorbance in the visible region. Small HOMO-LUMO energy gaps were observed in all investigated dyes. The present calculations on these dyes (1-6) offer an understanding of the direction of charge transfer (CT) and how NLO behavior can be explained. The aniline-to-halo phenyl CT, caused by the combination of the donor amino group and the acceptor halo group, could be a reason for NLO behavior of these sorts of compounds. These compounds exhibit significant molecular second-order NLO responses, especially dyes (6) and (5), with second-order polarizability determined to be approximately 4600 a.u.