Electronic Friction Near Metal Surface: Incorporating Nuclear Quantum Effect with Ring Polymer Molecular Dynamics

Abstract

Molecular dynamics with electronic friction (MDEF) approach can describe nonadiabatic effects accurately at metal surfaces in the weak nonadiabatic limit. That being said, MDEF treats nuclear motion classically, such that the nuclear quantum effects are missing completely in the approach. To address this limitation, we combine electronic friction with Ring Polymer Molecular Dynamics (RPMD). In particular, we apply the averaged electronic friction from the metal surface to the centroid mode of the ring polymer. We benchmark our approach against quantum dynamics to show that electronic friction with RPMD (EF-RPMD) can capture zero-point energy as well as transition dynamics accurately. In addition, we show EF-RPMD can correctly predict the electronic transfer rate near metal surfaces in the tunneling limit as well as the barrier crossing limit. We expect our approach will be very useful to study nonadiabatic dynamics near metal surface when nuclear quantum effects become essential.

References in corpus (10)

• Efficient stochastic thermostatting of path integral molecular dynamics
• Real-time path integral approach to nonequilibrium many-body quantum system
• Hierarchical Quantum Master Equation Approach to Electronic-Vibrational Coupling in Nonequilibrium Transport through Nanosystems
• Current-induced atomic dynamics, instabilities, and Raman signals: Quasi-classical Langevin equation approach
• Ab-initio tensorial electronic friction for molecules on metal surfaces: nonadiabatic vibrational relaxation
• Mode specific electronic friction in dissociative chemisorption on metal surfaces: H${}_2$ on Ag(111)
• Simultaneous Deep Tunneling and Classical Hopping for Hydrogen Diffusion on Metals
• Unraveling current-induced dissociation mechanisms in single-molecule junctions
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications

Cited by in corpus (3)

• Quantum rates in dissipative systems with spatially varying friction
• Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction
• A semiclassical nonequilibrium Green's Function approach to electron transport in systems exhibiting electron-phonon couplings