Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 126, Issue 10, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.2566637
Keywords
-
Ask authors/readers for more resources
The common density functionals for the exchange-correlation energy make serious self-interaction errors in the molecular dissociation limit when real or spurious noninteger electron numbers N are found on the dissociation products. An M-electron self-interaction-free functional for positive integer M is one that produces a realistic linear variation of total energy with N in the range of M-1 < N <= M, and so can avoid these errors. This desideratum is a natural generalization to all M of the more familiar one of one-electron self-interaction freedom. The intent of this paper is not to advocate for any functional, but to understand what is required for a functional to be M-electron self-interaction-free and thus correct even for highly stretched bonds. The original Perdew-Zunger self-interaction correction (SIC) and our scaled-down variant of it are exactly one- and nearly two-electron self-interaction-free, but only the former is nearly so for atoms with M>2. Thus all these SIC's produce an exact binding energy curve for H-2(+), and an accurate one for He-2(+), but only the unscaled Perdew-Zunger SIC produces an accurate one for Ne-2(+), where there are more than two electrons on each fragment Ne+0.5. We also discuss LiH+, which is relatively free from self-interaction errors. We suggest that the ability of the original and unscaled Perdew-Zunger SIC to be nearly M-electron self-interaction-free for atoms of all M stems in part from its formal resemblance to the Hartree-Fock theory, with which it shares a sum rule on the exchange-correlation hole of an open system.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available