Computer simulation of the cage effect in the photodissociation of bromine molecules in the presence of N2 at high pressures

Abstract

The classical trajectory technique has been used to study the caging process associated with the photolysis of bromine molecules in the presence of nitrogen. Calculations have been carried out at a number of gas densities and photon energies, and in order to simplify the problem the nitrogen molecules have been treated as rigid rotors. An analysis of the trajectories reveals that only one of the subdivisions of the primary cage effect (immediate primary) shows a strong dependence on both gas density and photon energy. Other types of cage event appear to take place between atoms which are almost in thermal equilibrium with the solvent.