Photodissociation Dynamics of the Collinear Van Der Waals Complex NeBr2(B, ν=14-34)

Abstract

We perform trajectory-based simulations of the dissociative dynamics of the collinear van der Waals complex NeBr2(B,ν) following photoexcitation to the B electronic state and for varying vibrational excitations of the dihalogen molecule in the range ν=14-34. The quantum dynamics of unimolecular decay is mapped onto a classical-like dynamics in an extended phase space. This methodology allows us to compute the time-dependent dissociation probability, intramolecular energy transfer mechanisms, and transient vibrational state distributions of the linear triatomic system, which are challenging to access experimentally using modern pump-probe spectroscopy techniques. The computed quantities can be used to refine interaction potential models at collinear geometries, which are less well characterized than the T-shaped isomer.