Dynamic Sampling of Liquid Metal Structures for Theoretical Studies on Catalysis

Liquid metals have recently emerged as promising catalysts that can outcompete their solid counterparts for many reactions. Although theoretical modelling is extensively used to improve solid-state catalysts, there is currently no way to capture the interactions of adsorbates with a dynamic liquid metal. We propose a new approach based on ab initio molecular dynamics sampling of an adsorbate on a liquid catalyst. Using this approach, we describe time-resolved structures for formate adsorbed on liquid Ga-In, and for all intermediates in the methanol oxidation pathway on Ga-Pt. This yields a range of accessible adsorption energies that take into account the at-temperature motion of the liquid metal. We find that a previously proposed pathway for methanol oxidation on Ga-Pt results in unstable intermediates on a dynamic liquid surface, and propose that H desorption must occur during the path. The results showcase a more accurate way to treat liquid metal catalysts in this emerging field.