Nonadiabatic Dynamics Simulations of Excited-state Proton Transfer

Morgan Hammer, University of Illinois at Urbana-Champaign

Excited-state charge transfer reactions are important in the conversion of solar energy into chemical energy. Better understanding of the non-equilibrium dynamics that govern the transfer of electrons and protons in the excited state can aid the rational design of devices for solar fuel production and optoelectronics. We have performed nonadiabtic dynamics with fewest-switches surface hopping (FSSH) simulations on an excited-state intramolecular proton-transfer (ESIPT) dye to determine the role of solvent relaxation in driving proton transfer. On-the-fly electronic structure calculations were done using FOMO-CASCI with a semi-empirical Hamiltonian that was reparameterized to reproduce key features of the relevant excited states computed at the CASSCF/CASPT2 level of theory. Our goal is to help explain trends in how the rate of ESIPT varies with solvent.

Abstract Author(s): M. Hammer