Relevance of coordinate and particle-number scaling in density functional theory

Abstract

We discuss a $\beta$-dependent family of electronic density scalings of the form $n_{\lambda }(\mathbb{R})={\lambda }^{3\beta +1}n({\lambda }^{\beta }\mathbb{R})$ in the context of density functional theory. In particular, we consider the following special cases: the Thomas-Fermi scaling ($\beta =1/3$ and $\lambda \gg 1$), which is crucial for the semiclassical theory of neutral atoms; the uniform-electron-gas scaling ($\beta =-1/3$ and $\lambda \gg 1$), that is important in the semiclassical theory of metallic clusters; the homogeneous density scaling ($\beta =0$) which can be related to the self-interaction problem in density functional theory when $\lambda \le 1$; the fractional scaling ($\beta =1$ and $\lambda \le 1$), that is important for atom and molecule fragmentation; and the strong-correlation scaling ($\beta =-1$ and $\lambda \gg 1$) that is important to describe the strong correlation limit. The results of our work provide evidence for the importance of this family of scalings in semiclassical and quantum theory of electronic systems, and indicate that these scaling properties must be considered as important constraints in the construction of new approximate density functionals. We also show, using the uniform-electron-gas scaling, that the curvature energy of metallic clusters is related to the second-order gradient expansion of kinetic and exchange-correlation energies.

13 pages, 3 figures, accepted for publication on PRA

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• Frozen density embedding with non-integer subsystems' particle numbers
• Improving the applicability of the Pauli kinetic energy density based semilocal functional for solids
• Hartree potential dependent exchange functional
• Nonlocal Orbital-Free Kinetic Energy Functional from the Jellium-with-Gap Model for Finite Systems