Self-interaction in natural orbital functional theory
- Resource Type
- Authors
- John E. Harriman; John M. Herbert
- Source
- Chemical Physics Letters. 382:142-149
- Subject
- Density matrix
education.field_of_study
Chemistry
Population
General Physics and Astronomy
Hartree
Electronic structure
Potential energy
Fock space
Atomic orbital
Quantum mechanics
Physical and Theoretical Chemistry
Atomic physics
Valence electron
education
- Language
- ISSN
- 0009-2614
Spurious self-interaction is shown to be responsible for essentially exact H2 potential energy curves calculated using simple one-electron density matrix functionals. For molecules with more than two electrons, bond-stretching potentials are unrealistically shallow due to overcorrelation that is most severe in the separated-atom limit. In addition, too much population is shifted into orbitals beyond the formal valence shell. Both problems are remedied by a facile self-interaction correction. At large internuclear distance, the corrected potentials are superior to those obtained from Hartree– Fock and density functional theories. 2003 Elsevier B.V. All rights reserved.