We present a Thomas-Fermi-inspired density scaling under which electron densities of atomic, molecular, or condensed matter become both large and slowly varying, so that semiclassical approximations and second-order density gradient expansions are asymptotically exact for the kinetic and exchange energies. Thus, even for atoms and molecules, density-functional approximations should recover the universal second-order gradient expansions in this limit. We also explain why common generalized gradient approximations for exchange do not.

It was shown by J. P. Perdew, R. G. Parr, M. Levy, and J. L. Balduz [Phys. Rev. Lett. 49, 1691 (1982)]; J. P. Perdew and M. Levy [Phys. Rev. Lett. 51, 1884 (1983)]; and L. J. Sham and M. Schlüter [Phys. Rev. Lett. 51, 1888 (1983)] that the exact Kohn-Sham exchange-correlation potential $v_{\text{xc}}\left(\vec{r}\right)$ of an open system may jump discontinuously as the particle number crosses an integer, with important physical consequences. The original derivations of the size and nature of the discontinuity rely on an implicit assumption that, when $N\to J$ from above and below, the effective potential of the interacting system with particle number $N$ becomes identical (modulo a constant) to the effective potential at an integer particle number $J$ so that the Kohn-Sham orbitals change continuously as $N$ passes through $J$ at fixed external potential. We prove under mild assumptions that the noninteracting kinetic energy of the interacting system is a continuous function of the particle number (as is the density itself), and hence argue that the original assumption is likely correct; if so, then all energy components are continuous. A rigorous proof of the existence and size of the $v_{\text{xc}}$ discontinuity is presented in the special case where the particle number crosses 1, by showing that, even when the Levy-Lieb constrained search for a minimum kinetic energy expectation value is taken to go over ensembles instead of wave functions, the noninteracting kinetic energy is still given by the von Weizsäcker functional for all densities with real particle number $N$ between 0 and 2 inclusive. We also prove that the von Weizsäcker functional is a lower bound on the ensemble-search noninteracting kinetic energy for all real $N>2$. To illustrate the $v_{\text{xc}}$ discontinuity and related results, we construct an analytic model density for the ${\text{H}}^{-}$ ion and plot the exchange-correlation potential as the particle number approaches 1 from above and below, and 2 from below. Finally, we discuss the behavior of the free-electron continuum as the particle number crosses an integer and the case where the particle number of a hydrogen or helium atom crosses $J=2$, the maximum number of electrons they can bind.

The selection of basic variables in current-density-functional theory and formal properties of the resulting formulations are critically examined. Focus is placed on the extent to which the Hohenberg-Kohn theorem, constrained-search approach, and Lieb's formulation (in terms of convex and concave conjugation) of standard density-functional theory can be generalized to provide foundations for current-density-functional theory. For the well-known case with the gauge-dependent paramagnetic current density as a basic variable, we find that the resulting total energy functional is not concave. It is shown that a simple redefinition of the scalar potential restores concavity and enables the application of convex analysis and convex (or concave) conjugation. As a result, the solution sets arising in potential-optimization problems can be given a simple characterization. We also review attempts to establish theories with the physical current density as a basic variable. Despite the appealing physical motivation behind this choice of basic variables, we find that the mathematical foundations of the theories proposed to date are unsatisfactory. Moreover, the analogy to standard density-functional theory is substantially weaker as neither the constrained-search approach nor the convex analysis framework carry over to a theory making use of the physical current density.

We present an analysis of the dispersion interaction energy and forces in density-functional theory from the point of view of the adiabatic connection between the Kohn–Sham non-interacting and fully interacting systems. Accurate coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] densities are computed for the helium dimer and used to construct the exchange-correlation potential of Kohn–Sham theory, showing agreement with earlier results presented for the Hartree–Fock–Kohn–Sham method [M. Allen and D. J. Tozer, J. Chem. Phys. 117, 11113 (2002)10.1063/1.1522715]. The accuracy of the methodology utilized to determine these solutions is checked by calculation of the Hellmann–Feynman forces based on the Kohn–Sham densities, which are compared with analytic CCSD(T) forces. To ensure that this comparison is valid in a finite atomic-orbital basis set, we employ floating Gaussian basis functions throughout and all results are counterpoise corrected. The subtle charge-rearrangement effects associated with the dispersion interaction are highlighted as the origin of a large part of the dispersion force. To recover the exchange-correlation components of the interaction energy, adiabatic connections are constructed for the supermolecular system and for its constituent atoms; subtraction of the resulting adiabatic-connection curves followed by integration over the interaction strength recovers the exchange-correlation contribution relevant to the density-functional description of the dispersion interaction. The results emphasize the long-ranged, dynamically correlated nature of the dispersion interaction between closed-shell species. An alternative adiabatic-connection path is also explored, where the electronic interactions are introduced in a manner that emphasizes the range of the electronic interactions, highlighting their purely long-ranged nature, consistent with the success of range-separated hybrid approaches in this context.