Non-Adiabatic Quantum Molecular Dynamics with Detailed Balance

Abstract

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum states. Such conditions occur in many research areas, including chemistry at metal surfaces, radiation damage of materials, and warm dense matter physics. The classical atomic motions are governed by stochastic Langevin-like equations, while the quantum electron dynamics is described by a master equation for the populations of the electronic states. These working equations are obtained from a first-principle derivation. Remarkably, unlike the widely used Ehrenfest and surface-hopping methods, the approach naturally satisfies the principle of detailed balance at equilibrium and, therefore, can describe the evolution to thermal equilibrium from an arbitrary initial state. In addition, unlike other schemes, there is no need to explicitly propagate wave functions in time.

5 pages, 0 figure, to be submitted

References in corpus (4)

• 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
• Born-Oppenheimer Dynamics, Electronic Friction, and the Inclusion of Electron-Electron Interactions
• Robust non-adiabatic molecular dynamics for metals and insulators

Cited by in corpus (5)

• Electron-phonon coupling in metals at high electronic temperatures
• First-Principles Determination of Electron-Ion Couplings in the Warm Dense Matter Regime
• Theory of the electron-ion temperature relaxation rate spanning the hot solid metals and plasma phases
• A Kinetic Model for Electron-Ion Transport in Warm Dense Matter
• Mixed quantum-classical approach to model non-adiabatic electron-nuclear dynamics: Detailed balance and improved surface hopping method