Hartree-Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals.
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.
Janesko
Benjamin G
BG
Department of Chemistry, Rice University, Houston, Texas 77005, USA. bjanesko@rice.edu
Scuseria
Gustavo E
GE
D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory