Scientific article
English

Nuclear cusps and singularities in the nonadditive kinetic potential bifunctional from analytical inversion

Published inPhysical review, A, vol. 106, no. 4, p. 1-12; 042812
Publication date2022-10-17
First online date2022-10-17
Abstract

The nonadditive kinetic potential 𝑣NAD is a key quantity in density-functional theory (DFT) embedding methods, such as frozen density embedding theory and partition DFT. 𝑣NAD is a bifunctional of electron densities 𝜌B and 𝜌tot=𝜌A+𝜌B. It can be evaluated using approximate kinetic-energy functionals, but accurate approximations are challenging. The behavior of 𝑣NAD in the vicinity of the nuclei has long been questioned, and singularities were seen in some approximate calculations. In this article, the existence of singularities in 𝑣NAD is analyzed analytically for various choices of 𝜌B and 𝜌tot, using the nuclear cusp conditions for the density and Kohn-Sham potential. It is shown that no singularities arise from smoothly partitioned ground-state Kohn-Sham densities. We confirm this result by numerical calculations on diatomic test systems HeHe, HeLi+, and H2, using analytical inversion to obtain a numerically exact 𝑣NAD for the local density approximation. We examine features of 𝑣NAD which can be used for development and testing of approximations to 𝑣NAD⁡[𝜌B,𝜌tot] and kinetic-energy functionals.

Keywords
  • Density functional theory
  • Electronic structure of atoms & molecules
  • Atomic, molecular & optical
  • Condensed matter, materials & applied physics
Funding
  • Australian Research Council (ARC) - Discovery Projects - Grant ID: DP200100033 [DP200100033]
  • Australian Research Council (ARC) - ARC Future Fellowships - Grant ID: FT210100663 [FT210100663]
Citation (ISO format)
BANAFSHEH, Mojdeh et al. Nuclear cusps and singularities in the nonadditive kinetic potential bifunctional from analytical inversion. In: Physical review, A, 2022, vol. 106, n° 4, p. 1–12. doi: 10.1103/PhysRevA.106.042812
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Article (Published version)
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ISSN of the journal2469-9926
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