Quantum Dynamics with Electronic Friction

TL;DR

This paper develops a comprehensive quantum theory of electronic friction using exact electron-nuclear wavefunction factorization, revealing how Berry's phase effects can persist in dissipative molecular systems on metallic surfaces.

Contribution

It introduces a non-linear Schrödinger equation for nuclei including friction, removing previous pseudo-magnetic terms, and predicts observable geometric phase effects in electronic friction contexts.

Findings

Friction kernel matches previous mixed quantum-classical results.

Pseudo-magnetic contributions are eliminated in the new formulation.

Berry's phase effects can be observed despite electronic friction.

Abstract

A theory of electronic friction is developed using the exact factorization of the electron-nuclear wavefunction. No assumption is made regarding the electronic bath, which can be made of independent or interacting electrons, and the nuclei are treated quantally. The ensuing equation of motion for the nuclear wavefunction is a non-linear Schr\"{o}dinger equation including a friction term. The resulting friction kernel agrees with a previously derived mixed quantum-classical result by Dou, Miao \& Subotnik (\emph{Phys. Rev. Lett.} \textbf{119}, 046001 (2017)), except for a \emph{pseudo}-magnetic contribution in the latter that is here removed. More specifically, it is shown that the electron dynamics generally washes out the\emph{ gauge} fields appearing in the adiabatic dynamics. However, at T=0 K, the \emph{pseudo}-magnetic force is fully re-established in the typical situation where the electrons respond rapidy on the slow time-scale of the nuclear dynamics (Markov limit). Hence, we predict Berry's phase effects to be observable also in the presence of electronic friction, and non-trivial geometric phases should be attainable for molecules on metallic magnetic surfaces.