Photoinduced dynamics of the valence states of ethene: a six-dimensional potential-energy surface of three electronic states with several conical intersections

摘要

A six-dimensional analytic potential-energy surface of the three valence states (N, V, Z) of ethene has been constructed on the basis of complete-active-space ab initio calculations and ab initio calculations with perturbation theory of second order based on a complete active reference space. The nuclear coordinate space is spanned by the torsion, the C-C stretch coordinate, the left and right pyramidalization and the symmetric and antisymmetric scissor coordinates. The C-H stretch coordinates and the CH_2 rocking angles are kept frozen at their ground-state equilibrium value. A diabatic representation of the valence states of ethene has been constructed within the framework of a Huckel-type model. The diabatic potential-energy elements are represented as analytic functions of the relevant coordinates. The parameters of the analytic functions have been determined by a least-squares fit of the eigenvalues fo the diabatic potential-energy matrix to the ab initio data for one-dimensional and two-dimensional cuts of the six-dimensional surface. As a function of the torsion, the analytic potential-energy surface describes the intersections of the V and Z states for torsional angles near 90 deg, which are converted into conical intersections by the antisymmetric scissor mode. As a function of pyramidalization of perpendicular ethene, it describes the intersections of the diabatic N and Z states, which are converted into conical intersections by displacements in the torsional mode. The analytic potential-energy surfaces can provide the basis for a quantum wave packet description of the internal conversion of photoexcited ethene to the electronic ground state via conical intersections.