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

Authors :
Pitts, Thomas C.
Bousiadi, Sofia
Gidopoulos, Nikitas I.
Lathiotakis, Nektarios N.
Source :
J. Chem. Phys. 158, 184105 (2023)
Publication Year :
2023

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, $\rho_{\rm rep}$, 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) $\rho_{\rm rep}$ integrates to $N-1$, where $N$ is the number of electrons, and (ii) $\rho_{\rm rep}\geq 0$ everywhere. In the present work, we introduce an effective ``screening'' amplitude, $f$, as the variational quantity, with the screening density being $\rho_{\rm rep}=f^2$. In this way, the positivity condition for $\rho_{\rm rep}$ 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.

Subjects

Subjects :
Physics - Chemical Physics

Details

Database :
arXiv
Journal :
J. Chem. Phys. 158, 184105 (2023)
Publication Type :
Report
Accession number :
edsarx.2304.10875
Document Type :
Working Paper
Full Text :
https://doi.org/10.1063/5.0143757