Effective Phase Space Representation of the Quantum Dynamics of Vibrational Predissociation of the ArBr₂(B,ν...

We perform trajectory-based simulations of the vibrational predissociation of the ArBr₂(B,ν=16···25) van der Waals triatomic complex, constrained to the T-shape geometry. To this aim, we employ a 2-fold mapping of the quantum dynamics into classical-like dynamics in an extended phase space. The effective phase space comprises two distinct sets of degrees of freedom, namely a collection of coupled harmonic oscillators and an ensemble of quantum trajectories. The time evolution of these variables represent bound and unbound motions of the quantum system, respectively. Quantum trajectories are propagated within the interacting trajectory representation. The comparison between the lifetimes of the predissociating complexes computed using the trajectory-based approach and the experimental results available for the target systems indicates that the present method is competitive with wavepacket propagation techniques. The competition between several simultaneous vibrational relaxation pathways was found to have a direct impact on the time scales of vibrational predissociation. Likewise, the analysis of the time evolution of the trajectories reveals the existence of regions in the effective phase space where transitions to vibrational states of higher energy are more likely to occur. The size and location of these regions influence the transient vibrational distributions and therefore the computed lifetimes. Furthermore, the mechanisms of energy redistribution along the dissociation coordinate are analyzed.