DFT computations and spectroscopic analysis of a pesticide: chlorothalonil

NIR FT-Raman and IR spectra of the biologically active molecule, chlorothalonil have been recorded and analyzed. The molecular geometry and vibrational wavenumbers of the title compound in the ground state have been calculated by density functional theory (DFT) with 6-31G(d) basis set. In order to obtain the information about the influence of intramolecular interaction on the molecule, the calculated geometries of chlorothalonil molecule was compared with the experimental data. The results of the optimized molecular structure gave clear evidence for the intramolecular charge transfer (ICT). Time-dependent density functional theory (TD-DFT) calculation of the electronic spectra has been performed and compared with the experimental UV-visible spectrum. Mulliken's net charges have been calculated and compared with the atomic natural charges. The effects of chlorine and cyanide group substituent in benzene ring in the vibrational wavenumbers have been analyzed. NBO analysis is useful to understand the intramolecular hyperconjugative interaction between lone pair Cl and sigma*(C-C) bond orbital.