Ab initio surface chemistry with chemical accuracy

First-principles calculations are a cornerstone of modern surface science and heterogeneous catalysis. However, accurate reaction energies and barrier heights are frequently inaccessible due to the approximations demanded by the large number of atoms. Here we combine developments in local correlation and periodic correlated wavefunction theory to solve the many-electron Schrödinger equation for molecules on surfaces with chemical accuracy, commonly defined as 1~kcal/mol. As a demonstration, we study water on the surface of \ce{Al2O3} and \ce{TiO2}, two prototypical and industrially important metal oxides for which we obtain converged energies at the level of coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], commonly known as the "gold-standard" in molecular quantum chemistry. We definitively resolve the energetics associated with water adsorption and dissociation, enabling us to address recent experiments and to analyze the errors of more commonly used approximate theories.