Electron Correlation Effects on the Longitudinal Polarizabilities and Second Hyperpolarizabilities of Polyenes: A Finite Field Study. (22nd July 2014)

• Record Type: Journal Article
• Authors: Li, Qingxu; Zhou, Xianju; Yin, Shiwei
• Other Names: Dou Yusheng Academic Editor.
• Is Part Of: International journal of photoenergy. Volume 2014(2014)
• Publication Date: 2014-07-22
• Subjects: Photochemistry -- Periodicals; Photobiology -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Photochimie; Photobiologie; Chimie physique et théorique; Chemistry, Physical and theoretical; Photobiology; Photochemistry; Electronic journals; Periodicals; 541.35
• DOI: 10.1155/2014/346272
• Languages: English
• ISSNs: 1110-662X

Abstract

Abstract : We carry out ab initio calculations, based on finite-field scheme, of the longitudinal polarizabilities (α L ) and second hyperpolarizabilities (γ L ) of conjugated polyenes, and study the effects of electron correlation, with second-order Moller-Plesset perturbation theory and coupled cluster with singles and doubles method. Calculations with density functional theory are also made to compare with wave-function based methods. Our study shows that electron correlation reduces linear longitudinal polarizability and enhances longitudinal second hyperpolarizability for short polyenes, but the effects decrease as the chain increases; choosing appropriate basis sets is important when quantitative results are required.