Ab-initio tensorial electronic friction for molecules on metal surfaces: nonadiabatic vibrational relaxation

Abstract

Molecular adsorbates on metal surfaces exchange energy with substrate phonons and low-lying electron-hole pair excitations. In the limit of weak coupling, electron-hole pair excitations can be seen as exerting frictional forces on adsorbates that enhance energy transfer and facilitate vibrational relaxation or hot-electron mediated chemistry. We have recently reported on the relevance of tensorial properties of electronic friction [Phys. Rev. Lett. 116, 217601 (2016)] in dynamics at surfaces. Here we present the underlying implementation of tensorial electronic friction based on Kohn-Sham Density Functional Theory for condensed phase and cluster systems. Using local atomic-orbital basis sets, we calculate nonadiabatic coupling matrix elements and evaluate the full electronic friction tensor in the classical limit. Our approach is numerically stable and robust as shown by a detailed convergence analysis. We furthermore benchmark the accuracy of our approach by calculation of vibrational relaxation rates and lifetimes for a number of diatomic molecules at metal surfaces. We find friction-induced mode-coupling between neighboring CO adsorbates on Cu(100) in a c(2x2) overlayer to be important to understand experimental findings.

arXiv comment16 pages, 8 figures, accepted to Physical Review B

References in corpus (20)

• The SIESTA method for ab initio order-N materials simulation
• Efficient index handling of multidimensional periodic boundary conditions
• Phonons and related properties of extended systems from density-functional perturbation theory
• Electron-phonon interactions and related physical properties of metals from linear-response theory
• First-principles method for electron-phonon coupling and electron mobility: Applications to 2D materials
• Unified description of inelastic propensity rules for electron transport through nanoscale junctions
• Quantum Thermodynamics: A Nonequilibrium Green's Functions Approach
• Improved tetrahedron method for the Brillouin-zone integration applicable to response functions
• Non-Adiabatic Potential-Energy Surfaces by Constrained Density-Functional Theory
• Fingerprints for spin-selection rules in the interaction dynamics of O2 at Al(111)
• Linear-Response Calculation of Electron-Phonon Coupling Parameters
• Electronic friction-based vibrational lifetimes of molecular adsorbates: Beyond the independent atom approximation
• Hot electron mediated desorption rates calculated from excited state potential energy surfaces
• Laser-like vibrational instability in rectifying molecular conductors
• Femtosecond laser driven molecular dynamics on surfaces: Photodesorption of molecular oxygen from Ag(110)
• Current-induced forces and hot-spots in biased nano-junctions
• Excited-state potential-energy surfaces of metal-adsorbed organic molecules from Linear Expansion Δ-Self-Consistent Field Density-Functional Theory (ΔSCF-DFT)
• Electronic damping of molecular motion at metal surfaces
• Bistability loss as key feature in azobenzene (non-)switching on metal surfaces
• Memory effects in non-adiabatic molecular dynamics at metal surfaces

Cited by in corpus (33)

• 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)
• i-PI 3.0: a flexible and efficient framework for advanced atomistic simulations
• Symmetry-Adapted High Dimensional Neural Network Representation of Electronic Friction Tensor of Adsorbates on Metals
• Current-induced forces for nonadiabatic molecular dynamics
• Electron-mediated phonon-phonon coupling drives the vibrational relaxation of CO on Cu(100)
• Adiabatic and Nonadiabatic Energy Dissipation during Scattering of Vibrationally Excited CO from Au(111)
• Energy, Momentum and Angular Momentum Transfer Between Electrons and Nuclei
• Machine Learning and Data-Driven Methods in Computational Surface and Interface Science
• Assessing mixed quantum-classical molecular dynamics methods for nonadiabatic dynamics of molecules on metal surfaces
• Non-Adiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence
• Vibrational Relaxation at a Metal Surface: Electronic Friction Versus Classical Master Equations
• Quantum Dynamics with Electronic Friction
• Efficient implementation and performance analysis of the independent electron surface hopping method for dynamics at metal surfaces
• Electronic Characterization of a Charge-Transfer Complex Monolayer on Graphene
• Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters
• Ultrafast adsorbate excitation probed with sub-ps resolution XAS
• Electronic friction in interacting systems
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory
• Electronic friction coefficients from the atom-in-jellium model for $Z=1-92$
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications
• Current-induced forces in nanosystems: A hierarchical equations of motion approach
• Electronic Friction Near Metal Surface: Incorporating Nuclear Quantum Effect with Ring Polymer Molecular Dynamics
• Non-Adiabatic Quantum Molecular Dynamics with Detailed Balance
• Nonadiabatic H-Atom Scattering Channels on Ge(111) Elucidated by the Hierarchical Equations of Motion
• Vibrational dynamics of CO on Pd(111) in and out of thermal equilibrium
• Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction
• Vibrational Energy Dissipation in Non-Contact Single-Molecule Junctions Governed by Local Geometry and Electronic Structure
• NQCDynamics.jl: A Julia Package for Nonadiabatic Quantum Classical Molecular Dynamics in the Condensed Phase
• An Antisymmetric Berry Frictional Force At Equilibrium in the Presence of Spin-Orbit Coupling
• Topological advantage for adsorbate chemisorption on conjugated chains
• Nonadiabatic dynamics at metal surfaces: fewest switches surface hopping with electronic relaxation
• Asymmetry and coverage dependence in two-pulse correlation measurements of CO photodesorption from Pd(111): Insights from theory