Theoretical study of the dissociation of HF+ in the B 2Σ+ state by quantum-mechanical methods

Publisher Website
Google Scholar
Abstract
The dissociative pathway of the HF+ molecular ion, initially in its B 2Σ+ electronic state, is studied by a full quantum‐mechanical technique. The vibronic time‐dependent wave function is expanded on the twelve lowest 2Σ+ electronic states computed by a limited configuration‐interaction calculation. The nuclear functions are projected on a monodimensional grid and the time‐evolution operator is represented by its (1,1) Padè approximant. The calculations are performed both in the adiabatic and in a semidiabatic representation of the electronic states. The decay pattern shows strong vibronic interactions often involving several states at a time. The results are compared with those obtained in a previous calculation, where the nuclear motion was treated by a classical trajectories approach.