English

Effective local potentials for density and density-matrix functional approximations with non-negative screening density

Chemical Physics 2023-05-22 v2

Abstract

A way to improve the accuracy of the spectral properties in density functional theory (DFT) is to impose constraints on the effective, Kohn-Sham (KS), local potential [J. Chem. Phys. {\bf 136}, 224109 (2012)]. As illustrated, a convenient variational quantity in that approach is the ``screening'' or ``electron repulsion'' density, ρrep\rho_{\rm rep}, corresponding to the local, KS Hartree, exchange and correlation potential through Poisson's equation. Two constraints, applied to this minimization, largely remove self-interaction errors from the effective potential: (i) ρrep\rho_{\rm rep} integrates to N1N-1, where NN is the number of electrons, and (ii) ρrep0\rho_{\rm rep}\geq 0 everywhere. In the present work, we introduce an effective ``screening'' amplitude, ff, as the variational quantity, with the screening density being ρrep=f2\rho_{\rm rep}=f^2. In this way, the positivity condition for ρrep\rho_{\rm rep} is automatically satisfied and the minimization problem becomes more efficient and robust. We apply this technique to molecular calculations employing several approximations in DFT and in reduced density matrix functional theory. We find that the proposed development is an accurate, yet robust, variant of the constrained effective potential method.

Keywords

Cite

@article{arxiv.2304.10875,
  title  = {Effective local potentials for density and density-matrix functional approximations with non-negative screening density},
  author = {Thomas C. Pitts and Sofia Bousiadi and Nikitas I. Gidopoulos and Nektarios N. Lathiotakis},
  journal= {arXiv preprint arXiv:2304.10875},
  year   = {2023}
}
R2 v1 2026-06-28T10:13:33.626Z