Quantum-Chemical Analysis of Electronic Excitation and Reactivity of Olefins and Dienes

Abstract

Results obtained in studying the structure of olefin and diene molecules, and complexes of these, in the ground and lower excited states by RHF, ROHF, GVB/DN, and 6-31G* quantum-chemical methods are presented. Attention is paid to the identity of the main structural and electronic parameters of triplet T1 and singlet S1 states forming a reactive fourfold spin-degenerate diradical equilibrium excited state (S·T)1 having the lowest energy. A new mechanism of cyclodimerization of ethylene and tetrafluoroethylene and anionic polymerization of dienes, involving the (S·T)1 states, is suggested.