Competition between adiabatic and nonadiabatic fragmentation pathways in the unimolecular decay of the ArI2(B) van der Waals complex

Abstract

The competition between vibrational and electronic predissociations of the ArI2(B) van der Waals complex has been studied using several dynamical computational methods: exact quantum wave-packet propagation, time-dependent golden rule, and quasiclassical trajectory with quantum jumps model. Five electronic states are considered using recent three-dimensional coupled surfaces obtained with a perturbative diatoms-in-molecules method. Final vibrational and electronic populations, predissociation rates, and absorption spectra have been computed for I2(B,v=18-24)<--I2(X,v=0) excitations within the complex. The contribution of vibrational predissociation into the total decay oscillates as a function of vibrational excitation due to intramolecular vibrational relaxation in a sparse-intermediate regime, which induces irregular variations of the total decay rate. Franck-Condon oscillations control the branching ratios of the individual electronic predissociation channels. However, since these oscillations are out of phase as a function of vibrational excitation, they have limited effect on the oscillatory behavior of the total predissociation rate. Comparison between exact quantum and perturbative golden rule calculations shows that vibrational predissociation has some impact on the electronic predissociation process and affects the final electronic distributions. On the contrary, vibrational product distributions are not significantly affected by the electronic predissociation. A classical description of the ArI2 dynamics provides an averaged picture of the competing predissociation processes, being better adapted for treating intermolecular vibrational relaxation in the statistical limit.