Molecular dynamics simulation of vibrational energy relaxation of highly excited molecules in fluids. I. General considerations

Methods of implementation of classical molecular dynamics simulations of mo derate size molecule vibrational energy relaxation and analysis of their re sults are proposed. Two different approaches are considered. The first is c oncerned with modeling a real nonequilibrium cooling process for the excite d molecule in a solvent initially at equilibrium. In addition to the solute total, kinetic, and potential energy evolution, that define the character of the process and the rate constant or relaxation time, a great deal of im portant information is provided by a normal mode specific analysis of the p rocess. Expressions for the decay of the normal mode energies, the work don e by particular modes, and the vibration-rotation interaction are presented . The second approach is based on a simulation of a solute-solvent system u nder equilibrium conditions. In the framework of linear nonequilibrium stat istical thermodynamics and normal mode representation of the solute several expressions for the rate constant are derived. In initial form, they are r epresented by integrals of the time correlation functions of the capacities of the solute-solvent interaction atomic or normal mode forces and include the solute heat capacity. After some approximations, which are adequate fo r specific cases, these expressions are transformed to combinations of thos e for individual oscillators with force-force time correlation functions. A s an attempt to consider a strongly nonequilibrium situation we consider a two-temperature model and discuss the reason why the rate constant can be i ndependent on the solute energy or temperature. Expressions for investigati on of the energy redistribution in the solvent are derived in two forms. On e of them is given in the usual form of a heat transfer equation with the s ource term describing the energy flux from the excited solute. The other fo rm describes the energy redistribution in the solvent in terms of capacity time correlation functions and can be more convenient if memory effects and spatial dispersion play an important role in energy redistribution in the solvent. (C) 1999 American Institute of Physics. [S0021-9606(99)51211-7].