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

Pitts, Thomas C.; Bousiadi, Sofia; Gidopoulos, Nikitas I.; Lathiotakis, Nektarios N.

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Authors

Thomas C. Pitts

Sofia Bousiadi

Nektarios N. Lathiotakis



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. 136, 224109 (2012)]. As illustrated, a convenient variational quantity in that approach is the “screening” or “electron repulsion” density, ρrep, 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 integrates to N −1, where N is the number of electrons, and (ii) ρrep ≥ 0 everywhere. In the present work, we introduce an effective “screening” amplitude, f , as the variational quantity, with the screening density being ρrep = f 2. In this way, the positivity condition for ρrep 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.

Citation

Pitts, T. C., Bousiadi, S., Gidopoulos, N. I., & Lathiotakis, N. N. (2023). Effective local potentials for density and density-matrix functional approximations with non-negative screening density. The Journal of Chemical Physics, 158(18), Article 184105. https://doi.org/10.1063/5.0143757

Journal Article Type Article
Acceptance Date Apr 20, 2023
Publication Date May 14, 2023
Deposit Date Apr 25, 2023
Publicly Available Date Apr 25, 2023
Journal The Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 158
Issue 18
Article Number 184105
DOI https://doi.org/10.1063/5.0143757

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