Investigating the Eley-Rideal recombination of hydrogen atoms on Cu (111) via a high-dimensional neural network potential energy surface

As a prototypical system for studying the Eley-Rideal (ER) mechanism at the gas-surface interface, the reaction between incident H/D atoms and pre-covered D/H atoms on Cu (111) has attracted much experimental and theoretical interest. Detailed final state-resolved experimental data have been available for about thirty-years, leading to the discovery of many interesting dynamical features. However, previous theoretical models have suffered from reduced-dimensional approximations and/or omitting energy transfer to surface phonons and electrons, or the high cost of on-the-fly ab initio molecular dynamics, preventing quantitative comparisons with experimental data. Herein, we report the first high-dimensional neural network potential (NNP) for this ER reaction based on first-principles calculations including all molecular and surface degrees of freedom. Thanks to the high efficiency of this NNP, we are able to perform extensive quasi-classical molecular dynamics simulations with the inclusion of the excitation of low-lying electron-hole pairs (EHPs), which generally yield good agreement with various experimental results. More importantly, the isotopic and/or EHP effects in total reaction cross-sections and distributions of the product energy, scattering angle, and individual ro-vibrational states have been more clearly shown and discussed. This study sheds valuable light on this important ER prototype and opens a new avenue for further investigations of ER reactions using various initial conditions, surface temperatures, and coverages in the future. © 2023 Royal Society of Chemistry. All rights reserved.