Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights

Abstract

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree-Fock electron densities, which has been known for ∼30 years. The conventional explanation is that the Hartree-Fock theory yields the more accurate density. This work presents a benchmark Kohn-Sham inversion of accurate coupled-cluster densities for the reaction H₂ + F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree-Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al. <i>J. Chem. Theory Comput.</i> 2023, 19, 532-543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.