MOLECULAR-DYNAMICS SIMULATION STUDIES OF SOLVENT CAGE EFFECTS ON PHOTODISSOCIATION IN CONDENSED PHASES

Molecular dynamics simulations have been applied to study solvent cage effects on photodissociation. The results show that when the solvent cages are sufficiently rigid, such as in Lennard-Jones glasses at low temperatures and high densities, or when solvent masses are substantially greater than solute masses, photoexcitation of a solute molecule to a repulsive excited state could lead to coherent oscillatory quasibound motion. This type of motion should be observable through femtosecond time-resolved spectroscopy. © 1994 American Institute of Physics.