Intersystem crossing at singlet conical intersections

Abstract

The energy of the lowest triplet state of organic molecules is intermediate between the ground state and the first excited singlet. At the S 1/ S 0 conical intersection, the two singlet states are degenerate. It is shown that for some molecules (ethylene, benzene, toluene and pyrrole) the T 1 state is also degenerate with the two singlet states. Moreover, the spin orbit coupling matrix element at this structure is necessarily large, so that intersystem crossing can be quite efficient. If the lowest triplet state is repulsive (as in the studied molecules) it may significantly contribute to the dissociation yield under certain experimental conditions.