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High first‐hyperpolarizabilities of thiobarbituric acid derivative‐based donor‐π‐acceptor nonlinear optical‐phores: Multiple theoretical investigations of substituents and conjugated bridges effect
Author(s) -
Liu Yidan,
Yuan Yizhong,
Tian Xiaohui,
Yuan Jianyong,
Sun Jinyu
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26176
Subject(s) - chemistry , basis set , excited state , conjugated system , dipole , acceptor , nonlinear optical , computational chemistry , absorption spectroscopy , oscillator strength , ground state , nonlinear system , atomic physics , spectral line , density functional theory , physics , organic chemistry , polymer , optics , quantum mechanics
A number of compounds including thiobarbituric acid derivative‐based acceptor unit and diverse donor moieties along with two types of π‐conjugated bridges have been constructed to aid in the design of the superior nonlinear optical (NLO) materials. The effect of varying the donor and bridge parts of this donor‐bridge‐acceptor system was analyzed in terms of structural and opto‐electronic parameters such as bond length alternation and ultraviolet‐visible absorption spectra. Various functionals with aug‐cc‐pVDZ basis set including B3LYP, PBE0, PBE38, BMK, CAM‐B3LYP, and ωB97XD were employed to calculate the static and dynamic first‐hyperpolarizabilities, and also the linear polarizabilities. Furthermore, the variation of the static first‐hyperpolarizabilities has been explained satisfactorily in the light of the sum‐over‐states method and two‐level model. The comprehensive study indicates that the coplanar compound D‐5 with the low electronic absorption energy, strongest oscillator strength paired with the largest ground, and excited state dipole moment difference generates a dramatical increase in its static and dynamic first‐hyperpolarizabilities, which would be the most worthwhile target for development as the NLO‐phores.