Abstract
Contemporary design of new organic non-linear optical (NLO) materials relies to a large extent on the understanding of molecular and electronic structure–property relationships revealed during the years by available computational approaches. The progress in theory—hand-in-hand with experiment—has enabled us to identify and analyze various physical aspects affecting the NLO responses, such as the environmental effects, molecular vibrations, frequency dispersion, and system dynamics. Although it is nowadays possible to reliably address these effects separately, the studies analyzing their mutual interplay are still very limited. Here, we employ density functional theory (DFT) methods in combination with an implicit solvent model to examine the solvent effects on the electronic and harmonic as well as anharmonic vibrational contributions to the static first hyperpolarizability of a series of push–pull α,ω-diphenylpolyene oligomers, which were experimentally shown to exhibit notable second-order NLO responses. We demonstrate that the magnitudes of both vibrational and electronic contributions being comparable in the gas phase significantly increase in solvents, and the enhancement can be, in some cases, as large as three- or even four-fold. The electrical and mechanical anharmonic contributions are not negligible but cancel each other out to a large extent. The computed dynamic solute NLO properties of the studied systems are shown to be in a fair agreement with those derived from experimentally measured electric-field-induced second-harmonic generation (EFISHG) signals. Our results substantiate the necessity to consider concomitantly both solvation and vibrational effects in modeling static NLO properties of solvated systems.
Funder
National Science Centre
Slovak Research and Development Agency
Scientific Grant Agency of the Slovak Republic
the Research and Development Operational Program
Subject
Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science
Cited by
2 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献