An accurate and efficient framework for modelling the surface chemistry of ionic materials

Abstract

Quantum-mechanical simulations can offer atomic-level insights into chemical processes on surfaces that are crucial to advancing applications in heterogeneous catalysis, energy storage and greenhouse gas sequestration. Unfortunately, achieving the accuracy needed for reliable predictions has proven challenging. Density functional theory, widely used for its efficiency, can be inconsistent, necessitating accurate methods from correlated wavefunction theory. But high computational demands and substantial user intervention have traditionally made correlated wavefunction theory impractical to carry out for surfaces. Here we present an automated framework that leverages multilevel embedding approaches to apply correlated wavefunction theory to the surfaces of ionic materials with computational costs approaching those of density functional theory. With this framework, we reproduce experimental adsorption enthalpies for a diverse set of 19 adsorbate–surface systems. We further resolve debates on the adsorption configuration of several systems, while offering benchmarks to assess density functional theory. This framework is open source, facilitating the routine application of correlated wavefunction theory to complex problems involving the surfaces of ionic materials.