Ultrafast charge transfer (CT) is among the most important and fundamental processes in the chemical, biological, and materials sciences. It is well-known that CT processes can be significantly modulated by the chemical environment in which they occur. Solvation, for instance, has been shown to drastically modify the transfer pathways, energetics, and lifetimes of CT states compared to gas-phase measurements. To accurately model any CT process occurring in non-vacuum conditions, one must account for the dynamical polarization of the electronically excited system by its chemical environment and vice versa. To this end, we have derived and implemented a first-principles electronic dynamics method with a time-dependent continuum embedding formalism that explicitly accounts for electrostatic solute-solvent interactions throughout the electronic trajectory. Both solute and solvent charge densities are propagated in time by coupling the equation of motion for the solvent, described by the time-dependent polarizable continuum model, to the evolution of the electronic degrees of freedom of the solute, described by the real-time time-dependent density functional theory. This coupled QM/continuum approach is capable of reproducing the effect of an electrically-polarizable environment on CT energies, mechanisms, and lifetimes.

First principles ultrafast charge transfer dynamics in solution: A time-domain TDDFT approach coupled with dielectric relaxation

249th National Meeting (2015)

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