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

J Chem Phys. 2008 Jun 28;128(24):244112. doi: 10.1063/1.2940738.

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Models, Chemical*
  • Models, Molecular
  • Quantum Theory*