DFT calculations in periodic boundary conditions of gas-phase acidities and of transition-metal anionic clusters: case study with carboxylate-stabilized ruthenium clusters - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Theoretical Chemistry Accounts: Theory, Computation, and Modeling Année : 2019

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

Résumé

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 ∼4kcal mol−1 mean average deviation (MAD) with respect to experiments and a ∼1kcal 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 Ru13 clusters, showing a linear correlation between adsorption energies and experimental gas-phase acidities.
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hal-02388707 , version 1 (07-12-2020)

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Roberto Gonzalez-Gomez, Iker Del rosal, Karine Philippot, Romuald Poteau. DFT calculations in periodic boundary conditions of gas-phase acidities and of transition-metal anionic clusters: case study with carboxylate-stabilized ruthenium clusters. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2019, 138 (8), pp.95. ⟨10.1007/s00214-019-2484-4⟩. ⟨hal-02388707⟩
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