Imposing correct jellium response is key to predict the density response by orbital-free DFT

Journal Article · 21 December 2023 · Physical Review. B

DOI: https://doi.org/10.1103/physrevb.108.235168 · OSTI ID:2338043

Moldabekov, Zhandos A.  ^[1]; Shao, Xuecheng ^[2]; Pavanello, Michele  ^[2]; Vorberger, Jan  ^[3]; Graziani, Frank  ^[4]; Dornheim, Tobias  ^[1]

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1. Center for Advanced Systems Understanding (CASUS), Görlitz (Germany); Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Dresden (Germany)
2. Rutgers University, Newark, NJ (United States)
3. Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Dresden (Germany)
4. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Orbital-free density functional theory constitutes a computationally highly effective tool for modeling electronic structures of systems ranging from room-temperature materials to warm dense matter. Its accuracy critically depends on the employed kinetic energy (KE) density functional, which has to be supplied as an external input. In this work we consider several nonlocal and Laplacian-level KE functionals and use an external harmonic perturbation to compute the static density response at T = 0 K in the linear and beyond-linear response regimes. We test for the satisfaction of exact conditions in the limit of uniform densities and for how approximate KE functionals reproduce the density response of realistic materials (e.g., Al and Si) against the Kohn-Sham DFT reference, which employs the exact KE. The results illustrate that several functionals violate exact conditions in the uniform electron gas (UEG) limit. We find a strong correlation between the accuracy of the KE functionals in the UEG limit and in the strongly inhomogeneous case. This empirically demonstrates the importance of imposing the limit of UEG response for uniform densities and validates the use of the Lindhard function in the formulation of kernels for nonlocal functionals. This conclusion is substantiated by additional calculations for bulk aluminum (Al) with a face-centered cubic (fcc) lattice and silicon (Si) with an fcc lattice, body-centered cubic (bcc) lattice, and semiconducting crystal diamond state. The analysis of fcc Al, and fcc as well as bcc Si data follows closely the conclusions drawn for the UEG, allowing us to extend our conclusions to realistic systems that are subject to density inhomogeneities induced by ions.

• Research Organization: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
• Sponsoring Organization: USDOE National Nuclear Security Administration (NNSA); Federal Ministry of Education and Research (BMBF); Saxon State Parliament; European Research Council (ERC); Technische Universität Dresden; National Science Foundation (NSF)
• Grant/Contract Number: AC52-07NA27344
• OSTI ID: 2338043
• Report Number(s): LLNL-JRNL-861932; 1094156
• Journal Information: Physical Review. B, Journal Name: Physical Review. B Journal Issue: 23 Vol. 108; ISSN 2469-9950
• Publisher: American Physical Society (APS)Copyright Statement
• Country of Publication: United States
• Language: English