Assessing mixed quantum-classical molecular dynamics methods for nonadiabatic dynamics of molecules on metal surfaces

Abstract

Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional models for the scattering of diatomic molecules at metal surfaces based on recently published electronic structure data. We apply several MQC methods to investigate their ability to capture how nonadiabatic effects influence molecule-metal energy transfer during the scattering process. Specifically, we compare molecular dynamics with electronic friction, Ehrenfest dynamics, Independent Electron Surface Hopping, and the Broadened Classical Master Equation approach. In the case of Independent Electron Surface Hopping, we implement a simple decoherence correction approach and assess its impact on vibrationally-inelastic scattering. Our results show that simple, low-dimensional models can be used to qualitatively capture experimentally observed vibrational energy transfer and provide insight into the relative performance of different MQC schemes. We observe that all approaches predict similar kinetic energy dependence, but return different vibrational energy distributions. Finally, by varying the molecule-metal coupling, we can assess the coupling regime in which some MQC methods become unsuitable.

arXiv comment15 pages, 13 figures, accepted in JPCC

References in corpus (16)

• Robust and efficient configurational molecular sampling via Langevin Dynamics
• Hierarchical Quantum Master Equation Approach to Electronic-Vibrational Coupling in Nonequilibrium Transport through Nanosystems
• Ab-initio tensorial electronic friction for molecules on metal surfaces: nonadiabatic vibrational relaxation
• Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions
• Strong Vibrational Relaxation of NO Scattered from Au(111): Importance of an Accurate Adiabatic Potential Energy Surface
• Equivariant analytical mapping of first principles Hamiltonians to accurate and transferable materials models
• Current-induced bond rupture in single-molecule junctions
• Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates
• Nonadiabatic molecular dynamics simulation: An approach based on quantum measurement picture
• Evaluation of the nondiabaticity of quantum molecular dynamics with the dephasing representation of quantum fidelity
• Hierarchical quantum master equation approach to vibronic reaction dynamics at metal surfaces
• Current-induced dissociation in molecular junctions beyond the paradigm of vibrational heating: The role of anti-bonding electronic states
• Quantum Dynamics with Electronic Friction
• Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces
• Interpreting Ultrafast Electron Transfer on Surfaces with a Converged First-Principles Newns-Anderson Chemisorption Function
• Vibrationally resolved NO dissociative excitation cross sections by electron impact

Cited by in corpus (5)

• Machine Learning and Data-Driven Methods in Computational Surface and Interface Science
• Controlling Plasmonic Catalysis via Strong Coupling with Electromagnetic Resonators
• A Linearized Semiclassical dynamics study of the multi-quantum vibrational relaxation of NO scattering from a Au(111) Surface
• Nonadiabatic H-Atom Scattering Channels on Ge(111) Elucidated by the Hierarchical Equations of Motion
• Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction