A challenge for density functionals: Self-interaction error increases for systems with a noninteger number of electrons

Published

Journal Article

The difficulty of widely used density functionals in describing the dissociation behavior of some homonuclear and heteronuclear diatomic radicals is analyzed. It is shown that the self-interaction error of these functionals accounts for the problem - it is much larger for a system with a noninteger number of electrons than a system with an integer number of electrons. We find the condition for the erroneous dissociation behavior described by approximate density functionals: when the ionization energy of one dissociation partner differs from the electron affinity of the other partner by a small amount, the self-interaction error will lead to wrong dissociation limit. Systems with a noninteger number of electrons and hence the large amount of self-interaction error in approximate density functionals arise also in the transition states of some chemical reactions and in some charge-transfer complexes. In the course of analysis, we derive a scaling relation necessary for an exchange-correlation functional to be self-interaction free. © 1998 American Institute of Physics.

Full Text

Duke Authors

Cited Authors

  • Zhang, Y; Yang, W

Published Date

  • December 1, 1998

Published In

Volume / Issue

  • 109 / 7

Start / End Page

  • 2604 - 2608

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.476859

Citation Source

  • Scopus