The Static (Hyper) Polarizabilities of Push-Pull Polyenes: A Theoretic Study
Qingxu Li *
School of Science, Chongqing University of Posts and Telecommunications, 400065, Chongqing, P. R. China
Ziting Yong
School of Science, Chongqing University of Posts and Telecommunications, 400065, Chongqing, P. R. China
Yan Zeng
School of Science, Chongqing University of Posts and Telecommunications, 400065, Chongqing, P. R. China and Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, P. R. China
*Author to whom correspondence should be addressed.
Abstract
We have studied the static longitudinal polarizability, and first and second hyperpolarizabilities of push-pull conjugated polyenes (NH2-(CH=CH)N-NO2) within finite field scheme. Ab initio methods and density functional theory (DFT) are used to evaluate electron correlation effects. B3LYP and CAM-B3LYP are compared with second-order Møller-Plesset perturbation theory (MP2) and highly reliable coupled cluster theory with single and double excitations (CCSD). Our study shows CAM-B3LYP fails to predict correct correlation contributions, and MP2 is also unsatisfactory. CCSD is the only reliable computational tool to this day.
Keywords: Polarizability, first and second hyperpolarizabilities, electron correlation effects, MP2, CCSD, CAM-B3LYP