3-DIMENSIONAL WAVE-PACKET DYNAMICS ON VIBRONICALLY COUPLED DISSOCIATIVE POTENTIAL-ENERGY SURFACES

A scheme for calculating three-dimensional wave-packet dynamics on conically intersecting SIGMA- and PI-surfaces of a triatomic molecule is presented. General potentials are employed and all three nuclear degrees of freedom remaining after separation of the rotational motion (J = 0) are included. Difficulties in the treatment of the angular coordinate due to the different centrifugal potentials on both surfaces are removed by a suitable transformation of the Hamiltonian. The scheme is applied to study numerically dissociation dynamics starting from an excited repulsive SIGMA-electronic state which is vibronically coupled to a bound PI-state.