Nonequilibrium Green's functions and atom-surface dynamics: Simple views from a simple model system

TL;DR

This paper uses Non-equilibrium Green's functions to model ultrafast laser-induced atom-surface dynamics, benchmarking various approximations and exploring substrate effects, demonstrating NEGF's potential in surface science.

Contribution

It introduces a comprehensive NEGF-based approach to simulate atom-surface dynamics under ultrafast laser pulses, comparing exact solutions with various approximations and including substrate effects.

Findings

Exact solutions benchmark approximations

Ehrenfest approximation's validity in this context

Substrate de-excitation channels hinder desorption

Abstract

We employ Non-equilibrium Green's functions (NEGF) to describe the real-time dynamics of an adsorbate-surface model system exposed to ultrafast laser pulses. For a finite number of electronic orbitals, the system is solved exactly and within different levels of approximation. Specifically i) the full exact quantum mechanical solution for electron and nuclear degrees of freedom is used to benchmark ii) the Ehrenfest approximation (EA) for the nuclei, with the electron dynamics still treated exactly. Then, using the EA, electronic correlations are treated with NEGF within iii) 2nd Born and with iv) a recently introduced hybrid scheme, which mixes 2nd Born self-energies with non-perturbative, local exchange-correlation potentials of Density Functional Theory (DFT). Finally, the effect of a semi-infinite substrate is considered: we observe that a macroscopic number of de-excitation channels can hinder desorption. While very preliminary in character and based on a simple and rather specific model system, our results clearly illustrate the large potential of NEGF to investigate atomic desorption, and more generally, the non equilibrium dynamics of material surfaces subject to ultrafast laser fields.