Computer simulation studies in activated rate theory and interfacial charge transfer

Jay Bradley Straus, University of Pennsylvania


Classical activated rate processes are studied via both numerical and theoretical methods, including reactive flux simulations. Nonlinearities are introduced into the underlying Hamiltonian in order to examine the effect on accepted theories. These studies are then expanded to use nonlinearities in such a way as to replicate spatially dependent friction, and the impact of this on both theoretical and basic conceptual models is assessed. We then focus on a subset of activated rate processes, interfacial charge transfer. Molecular dynamics simulations are conducted of electron transfer in a model system at a water-metal interface, exploring the effect of solvent density inhomogeneities on the diabatic free energy curves. The rate of ferrous-ferric electron transfer at the water-metal interface is then examined via reactive flux calculations and the determination of adiabatic free energy curves in both the classical and quantum limits.

Subject Area


Recommended Citation

Straus, Jay Bradley, "Computer simulation studies in activated rate theory and interfacial charge transfer" (1994). Dissertations available from ProQuest. AAI9427623.