Static second hyperpolarizability of twisted ethylene: A comprehensive computational study

Abstract

Twisted conformations of ethylene molecule have diradical character and the second hyperpolarizability of these conformations is best described by the multiconfigurational self consistence field theory (MCSCF) wave function. Present calculation indicates that unrestricted density functional theory (UDFT) predicts second hyperpolarizability which is qualitatively correct for the intermediate diradical region. However, for the two extremities, i.e. rear diradical region and near diradical region, the second hyperpolarizability obtained by UDFT methods differ significantly from the MRCISD result. The BHHLYP and LC-BLYP ([Formula: see text]) results of [Formula: see text] are found to be in good agreement with the MRCISD result. Using the spin-projected UDFT methods almost similar results are obtained. The reasonably fair agreement between the calculated results of second hyperpolarizability obtained at the MRCISD and CASSCF(4,4) levels demonstrates that static electron correlation is the dominant feature of twisted ethylene.