English

Wave-function inspired density functional applied to the H$_2$/H$_2^+$ challenge

Materials Science 2018-10-19 v1 Chemical Physics

Abstract

We start from the Bethe-Goldstone equation (BGE) to derive a simple orbital-dependent correlation functional -- BGE2 -- which terminates the BGE expansion at the second-order, but retains the self-consistent coupling of electron-pair orrelations. We demonstrate that BGE2 is size consistent and one-electron "self-correlation" free. The electron-pair correlation coupling ensures the correct H2_2 dissociation limit and gives a finite correlation energy for any system even if it has a no energy gap. BGE2 provides a good description of both H2_2 and H2+_2^+ dissociation, which is regarded as a great challenge in density functional theory (DFT). We illustrate the behavior of BGE2 analytically by considering H2_2 in a minimal basis. Our analysis shows that BGE2 captures essential features of the adiabatic connection path that current state-of-the-art DFT approximations do not.

Keywords

Cite

@article{arxiv.1604.03929,
  title  = {Wave-function inspired density functional applied to the H$_2$/H$_2^+$ challenge},
  author = {Igor Ying Zhang and Patrick Rinke and Matthias Scheffler},
  journal= {arXiv preprint arXiv:1604.03929},
  year   = {2018}
}

Comments

14 pages, 7 figures

R2 v1 2026-06-22T13:31:46.874Z