English

Exchange-only virial relation from the adiabatic connection

Chemical Physics 2024-10-22 v2 Mathematical Physics math.MP Quantum Physics

Abstract

The exchange-only virial relation due to Levy and Perdew is revisited. Invoking the adiabatic connection, we introduce the exchange energy in terms of the right-derivative of the universal density functional w.r.t. the coupling strength λ\lambda at λ=0\lambda=0. This agrees with the Levy-Perdew definition of the exchange energy as a high-density limit of the full exchange-correlation energy. By relying on vv-representability for a fixed density at varying coupling strength, we prove an exchange-only virial relation without an explicit local-exchange potential. Instead, the relation is in terms of a limit (λ0\lambda \searrow 0) involving the exchange-correlation potential vxcλv_\mathrm{xc}^\lambda, which exists by assumption of vv-representability. On the other hand, a local-exchange potential vxv_\mathrm{x} is not warranted to exist as such a limit.

Cite

@article{arxiv.2310.19144,
  title  = {Exchange-only virial relation from the adiabatic connection},
  author = {Andre Laestadius and Mihály A. Csirik and Markus Penz and Nicolas Tancogne-Dejean and Michael Ruggenthaler and Angel Rubio and Trygve Helgaker},
  journal= {arXiv preprint arXiv:2310.19144},
  year   = {2024}
}
R2 v1 2026-06-28T13:05:17.524Z