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

journal contribution

posted on 2022-10-17, 15:09 authored by Christina Yeo, Minh Nguyen, Lee-Ping WangMany 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 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 ωB97X-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 RMSEs of hydricity calculations for organic molecules in acetonitrile and dimethyl sulfoxide were found to be <4 and <10 kcal/mol, respectively, for an experimental data set with a dynamic range of 20–150 kcal/mol.## History

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hydrogen gas synthesisdetermine statistical significancecarbon dioxide reductionakaike information criterionpredicting thermodynamic hydricitiespoint energy correctionsrmse rank orderingbenchmarking density functionals2 thermodynamic hydricity dependfree energy requiredexperimental data setd3 density functionalenergy correctionsdensity functionalsdensity functionalthermodynamic hydricityr >< supthree parameterstheoretical predictionstheoretical calculationssquared errorsolvent modelssolvent modelseveral parametersselecting moleculesorganic moleculeslinear fitsimportant quantityhydride anionhydricity calculationsgeometry optimizationfixed slopeeither ωb97xdynamic rangedimethyl sulfoxidedifferent combinationscomputational costbest compromisebasis setsbasis set10 kcal

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