Electron Correlation Effects on the Longitudinal Polarizabilities and Second Hyperpolarizabilities of Polyenes: A Finite Field Study

Abstract EN

We carry out ab initio calculations, based on finite-field scheme, of the longitudinal polarizabilities (αL) and second hyperpolarizabilities (γL) of conjugated polyenes, and study the effects of electron correlation, with second-order Moller-Plessetperturbation 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.