Quantum-Chemical Analysis of Electronic Excitation and Reactivity of Olefins and Dienes |
| |
Authors: | K K Kalnin'sh S G Semenov |
| |
Institution: | (1) Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia;(2) St. Petersburg State University, St. Petersburg, Russia |
| |
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 T
1 and singlet S
1 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. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|