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. 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 for a set of molecules with known experimental hydricity values, generate linear fits, and compare the R-squared, root-mean-squared error, and Akaike Information Criterion across different combinations of density functionals, basis sets, and solvent models. Based on these results we are able to quantify the accuracy of theoretical predictions of hydricity and recommend the parameters with the best compromise between accuracy and computational cost.


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Supplementary material

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Example input files
Example input files for each level of theory used. P01-P10 are TeraChem input files while P11 is a Q-Chem input file.
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Starting structures
.xyz files of the starting molecular structures.
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Tables of hydricity values
Tables containing all experimental and calculated hydricity values
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Levels of Theory
Table of all levels of theory used labeled by ID number
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Molecule information
Contains information about the charge and spin multiplicity of each molecule