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 towards advancing applications in heterogeneous catalysis, energy storage and green- house gas sequestration. Unfortunately, achieving the accuracy needed for reliable predictions has proven challenging. Density functional theory (DFT), widely used for its efficiency, can be inconsistent, neces- sitating accurate methods from correlated wave-function theory (cWFT). However, high computational demands and significant user intervention have traditionally made cWFT impractical to carry out for surfaces. Here, we present an automated framework that leverages multilevel embedding approaches to apply cWFT to the surfaces of ionic materials with computational costs approaching DFT. With this framework, we have reproduced 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 DFT. This framework is open-source, facilitating the routine application of cWFT to complex problems involving the surfaces of ionic materials.