Journal of Chemical Physics, Vol.106, No.17, 6923-6941, 1997
Nonadiabatic Molecular-Dynamics Simulation of Ultrafast Pump-Probe Experiments on I-2 in Solid Rare-Gases
Recent experimental studies of both A and B state photoexcitation of I-2 and the ensuing many-body dynamics in rare gas matrices by Apkarian and co-workers are simulated using the methods we presented in an earlier work combining nonadiabatic molecular dynamics with semiempirical diatomics-in-molecules (DIM) excited state electronic structure techniques. We extend our DIM methods to compute the ion pair states of the I-2-rare gas crystal system and use these states together with a model of the configurational dependence of the electronic dipole operator matrix elements to calculate the time resolved probe absorption signals in these pump - probe experiments using a simple golden rule result. Our computed signals are in remarkable agreement with experiments and we use our calculations to provide a detailed microscopic analysis of the channels to predissociation and recombination underlying these experiments.
Keywords:LIQUID TRANSITION REGION;ION-PAIR STATES;CHEMICAL-REACTIVITY;CONDENSED PHASE;PHOTODISSOCIATION-RECOMBINATION;IODINE PHOTODISSOCIATION;GEMINATE RECOMBINATION;VIBRATIONAL-RELAXATION;FEMTOSECOND DYNAMICS;STRUCTURED CONTINUUM