Molecular dynamics study of the photodissociation of OClO in bulk liquids

The electronic spectra and the photodissociation dynamics of OClO on the excited state in bulk water, acetonitrile, and ethanol are computed using classical molecular dynamics computer simulations. The trajectories are run on an ab initio potential energy surface of Peterson [J. Chem. Phys. 109, 8864 (1998)], which is fit to a global three-dimensional analytical surface. The calculated cage escape probability in these liquids seems to correlate with the vibrational relaxation rate of the parent molecule and is in reasonable agreement with experiments in water and acetonitrile, but somewhat overestimates the experimental probability in the case of ethanol. (C) 2002 American Institute of Physics.