title: Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states.
abstract: The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited statemolecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited statemolecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.
authors.affiliation: Center for Nonlinear Studies, Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: J A
authors.initials: JA
authors.lastname: Bjorgaard
authors.affiliation: Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: K A
authors.initials: KA
authors.lastname: Velizhanin
authors.affiliation: Center for Integrated Nanotechnologies, Center for Nonlinear Studies, and Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: S
authors.initials: S
authors.lastname: Tretiak