Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory

Abstract

Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modelling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to first-principles calculations of reaction rates in high-dimensional realistic systems. In more detail, we develop a method that we coin ring polymer instanton with explicit friction (RPI-EF), starting from the ring-polymer instanton formalism applied to a system-bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor, and then combine this method with the \textit{ab initio} electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between RPI-EF and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.

References in corpus (16)

• How to remove the spurious resonances from ring polymer molecular dynamics
• 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
• Elucidating the NuclearQuantum Dynamics of Intramolecular Double Hydrogen Transfer in Porphycene
• Derivation of instanton rate theory from first principles
• Simultaneous Deep Tunneling and Classical Hopping for Hydrogen Diffusion on Metals
• Electronic friction-based vibrational lifetimes of molecular adsorbates: Beyond the independent atom approximation
• Path-integral dynamics of water using curvilinear centroids
• A microscopic description of acid-base equilibrium
• On the calculation of quantum mechanical electron transfer rates
• Ultrafast Transient Dynamics of Adsorbates on Surfaces Deciphered: The Case of CO on Cu(100)
• Stability and superconductivity of lanthanum and yttrium decahydrides
• Mixed quantum-classical dynamics using collective electronic variables: A better alternative to electronic friction theories
• Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions
• Multistate ring polymer instantons and nonadiabatic reaction rates
• A general non-adiabatic quantum instanton approximation

Cited by in corpus (6)

• i-PI 3.0: a flexible and efficient framework for advanced atomistic simulations
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications
• Electronic Friction Near Metal Surface: Incorporating Nuclear Quantum Effect with Ring Polymer Molecular Dynamics
• Comparison of Matsubara dynamics with exact quantum dynamics for an oscillator coupled to a dissipative bath
• Quantum rates in dissipative systems with spatially varying friction
• Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction