Hartree-Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals

Abstract

Semilocal density functional theory predictions for the barrier heights of representative hydrogen transfer, heavy-atom transfer, and nucleophilic substitution reactions are significantly improved in non-self-consistent calculations using Hartree-Fock orbitals. Orbitals from hybrid calculations yield related improvements. These results provide insight into compensating for one-electron self-interaction error in semilocal density functional theory. © 2008 American Institute of Physics.