Theoretical and Computational Chemistry

Benchmarking Density Functionals, Basis Sets, and Solvent Models in Predicting Thermodynamic Hydricities of Organic Hydrides



Many renewable energy technologies, such as hydrogen gas synthesis and carbon dioxide reduction, rely on chemical reactions involving hydride anions (H-). When selecting molecules to be used in such applications, an important quantity to consider is the thermodynamic hydricity, which is the free energy required for a species to donate a hydride anion. Theoretical calculations of thermodynamic hydricity depend on several parameters, mainly the density functional, basis set, and solvent model. In order to assess the effects of the above three parameters, we carry out hydricity calculations with different combinations of density functionals, basis sets, and solvent models for a set of organic molecules with known experimental hydricity values. The data are analyzed by comparing the R^2 and root-mean-squared error (RMSE) of linear fits with a fixed slope of 1 and using the Akaike Information Criterion (AIC) to determine statistical significance of the RMSE rank ordering. Based on these results, we quantified the accuracy of theoretical predictions of hydricity and found that the best compromise between accuracy and computational cost was obtained by using the B3LYP-D3 density functional for the geometry optimization and free energy corrections, either wB97X-D3 or M06-2X-D3 for single point energy corrections, combined with a basis set no larger than def-TZVP and the C-PCM ISWIG solvation model. At this level of theory, the RMSE of hydricity calculations for organic molecules in acetonitrile and DMSO were found to be <4 kcal/mol and <10 kcal/mol respectively for an experimental data set with a dynamic range of 20-150 kcal/mol.

Version notes

Switched x and y axes for plots, examines effects of dispersion correction, fixed errors with AIC calculations, added M06-2X-D3 to selection of density functionals


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Supplementary material

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Supporting Information
Quantum chemistry software input files; tables of calculated free energies of hydricity half reaction and calculated hydricity; charge and spin multiplicities of donor and acceptor structures; effects of dispersion correction on accuracy; conformational change of molecule 26 after heterolytic C-H bond dissociation; comparison between hydricities of three molecules obtained in this work versus obtained in Ilic et. al.