Effects of Rotational Isomerism and Bond Length Alternation on Optical Spectra of FTC Chromophore in Solution

Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-E-(4-N,N-di(2-acetoxyethyl)-amino)-phenylene-(3,4-dibutyl)-thien-5-E-vinylg-5,5-dimethyl-2,5-dihydrofuran (FTC) in a few solvents have been studied using the time-dependent density functional theory in combination with thepolarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.