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

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 ∼ 4 kcal mol - 1 mean average deviation (MAD) with respect to experiments and a ∼ 1 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 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. [ABSTRACT FROM AUTHOR]