Barrierless Water Dissociation on Rare-Earth Sesquioxide Surfaces from First Principles

Abstract

Water dissociation on metal oxide surfaces is a key elementary step in heterogeneous catalysis, photocatalysis, and radiation chemistry, yet its mechanistic details on rare-earth (RE) sesquioxides remain poorly understood. Here, we investigate water dissociation on the (110) surfaces of three cubic bixbyite oxides, Sc$_2$O$_3$, Y$_2$O$_3$, and Lu$_2$O$_3$, using molecular dynamics combining ab initio calculations with on-the-fly machine-learning force field acceleration. By sampling 25 independent trajectories per material, we obtain an unbiased picture of the reaction landscape inaccessible to conventional static calculations. Two distinct dissociation pathways are identified: a conventional proximal mechanism with a small but finite barrier of $\sim$0.1 eV, and a previously unreported distal mechanism that is effectively barrierless and energetically preferred at both the adsorption and dissociation stages. The low barriers are consistent with the periodic array of inherently undercoordinated RE$^{3+}$ sites in the bixbyite lattice, suggesting that ordered intrinsic coordination defects play a role analogous to stochastic oxygen vacancies in conventional oxides.