Mixed quantum-classical dynamics using collective electronic variables: A better alternative to electronic friction theories

Abstract

An accurate description of nonadiabatic dynamics of molecular species on metallic surfaces poses a serious computational challenge associated with a multitude of closely-spaced electronic states. We propose a mixed quantum-classical scheme that addresses this challenge by introducing collective electronic variables. These variables are defined through analytic block-diagonalization applied to the time-dependent Hamiltonian matrix governing the electronic dynamics. We compare our scheme with the Ehrenfest approach and with a full-memory electronic friction model on a one-dimensional "adatom + atomic chain" model. Our simulations demonstrate that collective-mode dynamics with only few (2-3) electronic variables is robust and can describe a variety of situations: from a chemisorbed atom on an insulator to an atom on a metallic surface. Our molecular model also reveals that the friction approach is prone to unpredictable and catastrophic failures.

5 pages, 3 figures, Supplementary Info file available

References in corpus (4)

• Energy loss of atoms at metal surfaces due to electron-hole pair excitations: First-principles theory of "chemicurrents"
• Electron-hole pair creation by atoms incident on a metal surface
• Electronic friction-based vibrational lifetimes of molecular adsorbates: Beyond the independent atom approximation
• Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates

Cited by in corpus (8)

• Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions
• Mode specific electronic friction in dissociative chemisorption on metal surfaces: H${}_2$ on Ag(111)
• The universality of electronic friction II: Equivalence of the quantum-classical Liouville equation approach with von Oppen's nonequilibrium Green's function methods out of equilibrium
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
• High-order geometric integrators for representation-free Ehrenfest dynamics
• On the Breakdown of the Ehrenfest Method for Molecular Dynamics on Surfaces
• Ehrenfest dynamics accelerated with SPEED
• Topological advantage for adsorbate chemisorption on conjugated chains