Theoretical approaches for simulating the ultrafast dynamics of photoinduced proton-coupled electron transfer (PCET) will be presented.  The first approach is based on a dielectric continuum representation of the solvent.  The solvent polarization is mapped onto two collective solvent coordinates corresponding to the single electron and proton transfer reactions.  An ensemble of nonadiabatic surface hopping trajectories is propagated with Langevin dynamics on electron-proton vibronic free energy surfaces that depend on the two collective solvent coordinates.  The second approach is based on an explicit molecular representation of the solvent.  In this case, the surface hopping trajectories are propagated with Newtonian dynamics on electron-proton potential energy surfaces that are calculated on-the-fly with a multistate empirical valence bond potential.  Application of these approaches to model systems illustrates the impact of nonequilibrium solvent dynamics on the overall charge transfer process and provides an explanation for experimentally observed deuterium isotope effects.

Nonadiabatic dynamics of ultrafast photoinduced proton-coupled electron transfer reactions in solution

243rd National Meeting (2012)

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