Electronic structure and nonlinear optical properties of push-pull polyenes: theoretical investigation of benzodithia polyenals and dithiolene polyenals

Abstract

We report the results of ab initio Hartree-Fock calculations on the geometric and electronic structure and first-order (α) and second-order (β) molecular polarizabilities of a series of push-pull polyene molecules. The acceptor is in all cases an aldehyde group while the donor is either a benzodithia, a dithiolene, or a dithiolane group. The benzodithia polyenal compounds have recently been shown to present among the largest μ-β values ever measured. Theoretical results are found to be in excellent agreement with experimental data