CO$_2$ Dissociative Sticking on Cu(110)

TL;DR

This study uses density functional theory and neural network-parameterized potential energy surfaces to analyze CO$_2$ dissociation on Cu(110), revealing energy-dependent surface distortions and structures consistent with experimental observations.

Contribution

It introduces a combined computational approach to model CO$_2$ dissociation on Cu(110), capturing detailed surface dynamics and product structures at various energies and temperatures.

Findings

Dissociation probabilities agree with experimental data.

Surface distortions and Cu adatom formation occur at high impact energies.

High-energy dissociation leads to complex surface structures and increased oxygen coverage.

Abstract

In this work we investigate the dissociation of CO$_2$ on Cu(110) by performing density functional theory calculations using the vdW-DF2 exchange-correlation functional, with a potential energy surface parameterized using artificial neural networks. We computed quasi-classical trajectory calculations of molecular and dissociative adsorption probabilities as a function of the initial impact energy of the molecules and surface temperature, by comparing our results with available supersonic molecular beam experimental data for normal incidence. Concerning the general dependence of the molecular and dissociative adsorption probabilities on the initial translational energy of the molecules, our theoretical results agree with experiments. Also in agreement with experiments, we have found that dissociative adsorption is not affected by surface temperature between 50 and 400 K, for impact energies for which the dissociation probability is larger than $\sim 10^{-3}$. We have investigated the influence of impact energy and surface temperature on the final state of the dissociation products by extending the time integration of the reactive trajectories up to 10 ps. We have found that above $\sim 2.5$ eV and close to or above room temperature, CO$_2$ dissociation induces strong surface distortions including final structures involving Cu adatoms. The creation of Cu vacancy-adatom pairs is stimulated by the presence of both CO$_{ads}$ and O$_{ads}$ which interact strongly with the Cu adatoms and even give rise to unexpected (O-Cu-CO)$_{ads}$ linear moieties anchored to the surface by the dissociated O atom and involving a Cu adatom almost detached from the surface. These surface distortions produced by dissociation products of high energy CO$_2$ molecules at and above room temperature might explain recent experiments that have found a greater saturation oxygen coverage for high energy molecules.