The effect of diffusion on energy transfer from excited donor to acceptor molecules in liquid solutions is studied with particular attention focused on vibrational energy transfer between solute molecules in dilute solutions. Such processes are often discussed in the independent binary collision (IBC) framework and diffusion effects are assumed to be negligible. We introduce the concept of diffusive collisions (encounters between acceptor and donor molecule within an effective energy transfer range) and investigate the conditions under which the cross section for the energy transfer process may be affected by the cross section for the diffusive collision as opposed to the more common fast diffusion limit where the energy transfer is dominated by direct binary collisions. We conclude that while in most common situations vibrational energy transfer is indeed dominated by binary collision events, pronounced diffusion effects should exist at moderately high pressures. Explicit estimates are provided for the HCl/Xe system.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry