The Jahn–Teller effect in the ground electronic state of the tetrafluoromethane cation before dissociation: a promoter of the anisotropic fragmentation

Abstract

ABSTRACTThe role of multimode Jahn–Teller coupling effect on the anisotropic fragmentation of in its electronic state is investigated theoretically via an ab initio quantum dynamics study. The potential energy surfaces up to two-dimensions of nuclear coordinates are established from extensive electronic structure calculations. A higher order (seventh-order) diabatic vibronic coupling model Hamiltonian is necessary to mimic the ab initio potentials and thereby constructed. The theoretical results are in good agreement with experimental observations. A detail analysis of the relevant static aspects and the vibrational progressions under the structureless and broad vibronic band of are made. Present study suggests that the Jahn–Teller effect is operative before the dissociation of upon photoionisation and responsible for the experimentally measured anisotropic fragmentation in the electronic state of the title cation.