Constraining density functional approximations to yield self-interaction free potentials

Gidopoulos, N.I.; Lathiotakis, N.N.

Abstract

Self-interactions (SIs) are a major problem in density functional approximations and the source of serious divergence from experimental results. Here, we propose to optimize density functional total energies in terms of the effective local potential, under constraints for the effective potential that guarantee it is free from SI errors and consequently asymptotically correct. More specifically, we constrain the Hartree, exchange and correlation potential to be the electrostatic potential of a non-negative effective repulsive density of N − 1 electrons. In this way, the optimal effective potentials exhibit the correct asymptotic decay, resulting in significantly improved one-electron properties.

Citation

Gidopoulos, N., & Lathiotakis, N. (2012). Constraining density functional approximations to yield self-interaction free potentials. The Journal of Chemical Physics, 136(22), Article 224109. https://doi.org/10.1063/1.4728156

• Journal Article Type: Article
• Publication Date: Jun 14, 2012
• Deposit Date: May 14, 2013
• Publicly Available Date: Oct 15, 2014
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 136
• Issue: 22
• Article Number: 224109
• DOI: https://doi.org/10.1063/1.4728156