Surface Adsorption Energetics Studied with “Gold Standard” Wave-Function-Based Ab Initio Methods: Small-Molecule Binding to TiO₂(110)

Abstract

Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T)) is widely considered to be the "gold standard" of ab initio quantum chemistry. Using the domain-based pair natural orbital local correlation concept (DLPNO-CCSD(T)), these calculations can be performed on systems with hundreds of atoms at an accuracy of ∼99.9% of the canonical CCSD(T) method. This allows for ab initio calculations providing reference adsorption energetics at solid surfaces with an accuracy approaching 1 kcal/mol. This is an invaluable asset, not least for the assessment of density functional theory (DFT) as the prevalent approach for large-scale production calculations in energy or catalysis applications. Here we use DLPNO-CCSD(T) with embedded cluster models to compute entire adsorbate potential energy surfaces for the binding of a set of prototypical closed-shell molecules (H₂O, NH₃, CH₄, CH₃OH, CO₂) to the rutile TiO₂(110) surface. The DLPNO-CCSD(T) calculations show excellent agreement with available experimental data, even for the "infamous" challenge of correctly predicting the CO₂ adsorption geometry. The numerical efficiency of the approach is within 1 order of magnitude of hybrid-level DFT calculations, hence blurring the borders between reference and production technique.