DFT calculations in periodic boundary conditions of gas-phase acidities and of transition-metal anionic clusters: case study with carboxylate-stabilized ruthenium clusters

Abstract

The first part of this study aims at evaluating the accuracy of DFT calculations of acids and their conjugate bases in periodic boundary conditions and plane-wave basis sets. The resulting gas-phase acidities are compared to experimental data. Calculations done with the PBE functional are accurate, with a $$\sim 4\,\hbox {kcal mol}^{-1}$$ mean average deviation (MAD) with respect to experiments and a $$\sim 1\,\hbox {kcal mol}^{-1}$$ MAD with respect to non-periodic DFT calculations done in the aug-cc-pvtz basis set with the same functional. In the second part, the relative stability of $$\mathrm{Ru}_{13}^{-}$$ isomers is also successfully compared to previous calculations done using local basis sets (Waldt et al. in J Chem Phys 142:024319, 2015). Finally, several carboxylic acids and their conjugate bases are adsorbed on two Ru $$_{13}$$ clusters, showing a linear correlation between adsorption energies and experimental gas-phase acidities.