Understanding and correcting the self-interaction error in the electrical response of hydrogen chains

Adrienn Ruzsinszky, John P. Perdew, Gábor I. Csonka, Gustavo E. Scuseria, Oleg A. Vydrov

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

Semilocal density functionals such as the local-spin-density and generalized-gradient approximations are known to overestimate the polarizabilities and especially the hyperpolarizabilities of long-chain molecules, the latter by as much as a factor of 10 or more in model hydrogen chains. These quantities are much better predicted by exact-exchange methods such as Hartree-Fock or optimized effective potential. We show here that the semilocal functionals, after full or scaled-down Perdew-Zunger self-interaction correction (SIC), are about as good as the exact-exchange methods for these quantities. As is the case for the exact-exchange methods, SIC is fully nonlocal and exact for all one-electron densities, and (more relevantly to the electrical response) tends to maintain an integer number of electrons on each H2 chain unit to a greater extent than the semilocal functionals do. In this study, the SIC energy is minimized directly, without an optimized effective potential.

Original languageEnglish
Article number060502
JournalPhysical Review A - Atomic, Molecular, and Optical Physics
Volume77
Issue number6
DOIs
Publication statusPublished - Jun 20 2008

    Fingerprint

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this