Photochemistry of ethylene: a multireference configuration interaction investigation of the excited-state energy surfaces.
Multireference configuration interaction with singles and doubles (MR-CISD) calculations have been performed for the optimization of conical intersections and stationary points on the ethylene excited-state energy surfaces using recently developed methods for the computation of analytic gradients and nonadiabatic coupling terms. Basis set dependence and the effect of various choices of reference spaces for the MR-CISD calculations have been investigated. The crossing seam between the S0 and S1 states has been explored in detail. This seam connects all conical intersections presently known for ethylene. Major emphasis has been laid on the hydrogen-migration path. Starting in the V state of twisted-orthogonal ethylene, a barrierless path to ethylidene was found. The feasibility of ethylidene formation will be important for the explanation of the relative yield of cis and trans H2 elimination.
Barbatti
M
M
Institute for Theoretical Chemistry and Structural Biology, University of Vienna, A-1090 Vienna, Austria. mario.barbatti@univie.ac.at
Paier
J
J
Lischka
H
H