Negative Electronic Friction and Non-Markovianity in Nonequilibrium Quantum Systems.

Abstract

We address the connection between negative electronic friction and non-Markovian effects in the nonadiabatic vibrational dynamics of molecules interacting with metal surfaces under nonequilibrium conditions. We show that a generic nonequilibrium mechanism leading to negative Markovian electronic friction, where molecular vibrations couple directly to inelastic electronic transitions, also introduces significant non-Markovian contributions to the electronic friction. To demonstrate these ideas, we investigate nonequilibrium charge transport through a molecular nanojunction containing a vibrationally coupled donor-acceptor model, where negative electronic friction reflects driving of the vibrational mode beyond standard Joule heating. By comparison to numerically exact, fully quantum hierarchical equations of motion simulations, we verify that these non-Markovian effects have a significant impact on the nonequilibrium dynamics and even on the stability of the resulting Langevin equation.