Hartree–Fock orbitals significantly improve the reaction barrier heights predicted by semilocal density functionals
- 27 June 2008
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 128 (24) , 244112
- https://doi.org/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.Keywords
This publication has 51 references indexed in Scilit:
- Many-electron self-interaction error in approximate density functionalsThe Journal of Chemical Physics, 2006
- The 6-31B(d) Basis Set and the BMC-QCISD and BMC-CCSD Multicoefficient Correlation MethodsThe Journal of Physical Chemistry A, 2005
- A new parametrization of exchange–correlation generalized gradient approximation functionalsThe Journal of Chemical Physics, 2001
- Left-right correlation energyMolecular Physics, 2001
- Comparison of the Accurate Kohn−Sham Solution with the Generalized Gradient Approximations (GGAs) for the SN2 Reaction F- + CH3F → FCH3 + F-: A Qualitative Rule To Predict Success or Failure of GGAsThe Journal of Physical Chemistry A, 2000
- Benchmark calculations of chemical reactions in density functional theory: Comparison of the accurate Kohn–Sham solution with generalized gradient approximations for the H2+H and H2+H2 reactionsThe Journal of Chemical Physics, 1999
- Rationale for mixing exact exchange with density functional approximationsThe Journal of Chemical Physics, 1996
- A new direct ab initio dynamics method for calculating thermal rate constants from density functional theoryThe Journal of Chemical Physics, 1994
- Comparison of coupled-cluster results with a hybrid of Hartree–Fock and density functional theoryThe Journal of Chemical Physics, 1992
- Self-interaction correction to density-functional approximations for many-electron systemsPhysical Review B, 1981