Assessing the Accuracy of Density Functional Approximations for Predicting Hydrolysis Reaction Kinetics

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Abstract
Hydrolysis reactions are ubiquitous in biological, environmental, and industrial chemistry. Density functional theory (DFT) is commonly employed to study the kinetics and reaction mechanisms of hydrolysis processes. Here, we present a new data set, Barrier Heights for HydrOlysis - 36 (BH2O-36), to enable the design of density functional approximations (DFAs) and the rational selection of DFAs for applications in aqueous chemistry. BH2O-36 consists of 36 diverse organic and inorganic forward and reverse hydrolysis reactions with reference energy barriers ΔE‡ calculated at the CCSD(T)/CBS level. Using BH2O-36, we evaluate 63 DFAs. In terms of mean absolute error (MAE) and mean relative absolute error (MRAE), ωB97M-V is the best-performing DFA tested, while MN12-L-D3(BJ) is the best-performing pure (nonhybrid) DFA. Broadly, we find that range-separated hybrid DFAs are necessary to approach chemical accuracy (0.043 eV). Although the best-performing DFAs include a dispersion correction to account for long-range interactions, we find that dispersion corrections do not generally improve MAE or MRAE for this data set.
Funding Information
  • Basic Energy Sciences (DE-SC0021266)
  • National Energy Research Scientific Computing Center (DE-AC02-05CH11231)
  • Kavli Foundation
  • National Science Foundation (DGE 1752814)

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