Ab initio diradical/zwitterionic polarizabilities and hyperpolarizabilities in twisted double bonds.
We investigated the nature of the ground state and static response properties (mu, alpha, and beta) for a promising class of twisted pi-electron system nonlinear optical chromophores at the HF, B3LYP, MP2, and CASSCF levels. We report results for a substituted twisted ethylene and a larger tictoid analogue. Previous work has reported only a zwitterionic character for such tictoid species, however, (14,13) CASSCF calculations predict a ground-state diradical. At the HF, B3LYP, MP2, and (14,13) CASSCF levels, the values of beta are orders of magnitude smaller than those predicted by semiempirical methods.
Isborn
Christine M
CM
Department of Chemistry, University of Washington, Seattle, 98195-1700, USA.
Davidson
Ernest R
ER
Robinson
Bruce H
BH