文献类型：期刊文献

英文题名：Computational design of p-(dimethylamino)benzylidene-derived push-pull polyenes with high first-hyperpolarizabilities

作者：Liu, Yidan[1,2];Yuan, Yizhong[1,2];Tian, Xiaohui[1,2];Yuan, Jianyong[1,2];Sun, Jinyu[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab Adv Polymer Mat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China

年份：2020

卷号：22

期号：9

起止页码：5090

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20201108297038);WOS:【SCI-EXPANDED(收录号:WOS:000519248900023)】；

基金：The authors acknowledge the support from the Shanghai Leading Academic Discipline Project (No. B502), the Shanghai Key Laboratory Project (No. 08DZ2230500), and the National Natural Science Foundation of China (No. 21975073). Special thanks are given to Dr Hongshuai Wang for his academic and technical assistance.

语种：英文

外文关键词：Ultraviolet spectroscopy - Pinch effect - Bond length - Solvents - Bridges - Ground state

摘要：Multiple theoretical investigations on three new series of donor-bridge-acceptor substituted compounds are employed to aid in the design of NLO-phores with high first-hyperpolarizability beta. The effect of varying the acceptor (rhodanine, thiohydantoin and thiobarbituric acid derivative-based) and bridge parts of these D-pi-A systems was analyzed in terms of geometric and optoelectronic parameters such as bond length alternation, ground state dipole moments, HOMO and LUMO energies, UV-vis absorption spectra, transition dipole moments, and electronic absorption energies. Various functionals with the AUG-cc-pVDZ basis set including B3LYP, PBE38, and omega B97XD, and the Hartree-Fock method were employed to calculate beta values, and the solvent effect was also considered by employing the SMD model. The variation of first-hyperpolarizabilities has been explained satisfactorily in terms of the PBE38/AUG-cc-pVDZ level calculated spectroscopic properties in the light of the sum-over-states method and the two-level model. The comprehensive study indicates that the most worthwhile targets for development as NLO-phores are compounds that include a longer pi-bridge.