Non-adiabatic dynamics of electrons and atoms under non-equilibrium conditions

TL;DR

This paper introduces a comprehensive quantum-mechanical method for simulating non-adiabatic atomic and electronic dynamics under non-equilibrium conditions, capturing complex phenomena beyond simple vibrations.

Contribution

It develops an exact, partition-less approach combining path integrals and NEGF, enabling simulation of atomic movement beyond vibrations in non-equilibrium systems.

Findings

Derives an exact quantum Liouville equation for nuclei.

Formulates stochastic differential equations for atomic trajectories.

Potential applications include photo-induced reactions and atomic manipulation.

Abstract

An approach to non-adiabatic dynamics of atoms in molecular and condensed matter systems under general non-equilibrium conditions is proposed. In this method interaction between nuclei and electrons is considered explicitly up to the second order in atomic displacements defined with respect to the mean atomic trajectory. This method enables one to consider movement of atoms beyond their simple vibrations. Both electrons and nuclei are treated fully quantum-mechanically using a combination of path integrals applied to nuclei and non-equilibrium Green's functions (NEGF) to elections. Our method is partition-less: initially, the entire system is coupled and assumed to be at thermal equilibrium. Then, the exact application of the Hubbard-Stratanovich transformation in mixed real and imaginary times enables us to obtain, without doing any additional approximations, an exact expression for the reduced density matrix for nuclei and hence an effective quantum Liouville equation for them, both containing Gaussian noises. It is shown that the time evolution of the expectation values for atomic positions is described by an infinite hierarchy of stochastic differential equations for atomic positions and momenta and their various fluctuations. The actual dynamics is obtained by sampling all stochastic trajectories. It is expected that applications of the method may include photo-induced chemical reactions (e.g. dissociation), electromigration, atomic manipulation in scanning tunneling microscopy, to name just a few.