Related papers: Dissociation limit in Kohn-Sham density functional…
A rigorous derivation of the density functional in the Hohenberg-Kohn theory is presented. With no assumption regarding the magnitude of the electric coupling constant $e^2$ (or correlation), this work provides a firm basis for…
We generalize the exact strong-interaction limit of the exchange-correlation energy of Kohn-Sham density functional theory to open systems with fluctuating particle numbers. When used in the self-consistent Kohn-Sham procedure on…
We use the exact strong-interaction limit of the Hohenberg-Kohn energy density functional to approximate the exchange-correlation energy of the restricted Kohn-Sham scheme. Our approximation corresponds to a highly non-local density…
Two electrons at the threshold of ionization represent a severe test case for electronic structure theory. A pseudospectral method yields a very accurate density of the two-electron ion with nuclear charge close to the critical value.…
We introduced a new electron density n({\epsilon}) by projecting the spatial electron density n(r) onto the energy coordinate {\epsilon} defined with the external potential \upsion (r) of interest. Then, a density functional theory (DFT)…
We discuss energy densities in the strong-interaction limit of density functional theory, deriving an exact expression within the definition (gauge) of the electrostatic potential of the exchange-correlation hole. Exact results for small…
Self-consistent correlation potentials for H$_2$ and LiH for various inter-atomic separations are obtained within the random phase approximation (RPA) of density functional theory. The RPA correlation potential shows a peak at the bond…
We show that density functional theory within the RPA (random phase approximation for the exchange-correlation energy) provides a correct description of bond dissociation in H$_2$ in a spin-restricted Kohn-Sham formalism, i.e. without…
The exchange-correlation hole density of the infinitely stretched (dissociated) hydrogen molecule can be cast into a closed analytical form by using its exact wave function. This permits to obtain an explicit exchange-correlation energy…
Many approximations within density-functional theory spuriously predict that a many-electron system can dissociate into fractionally charged fragments. Here, we revisit the case of dissociated diatomic molecules, known to exhibit this…
Molecular dipole moments of analytic density-functional theory are investigated. The effect of element-dependent exchange potentials on these moments are examined by comparison with conventional quantum-chemical methods and experiment for…
Modern density functional theory (DFT) calculations employ the Kohn-Sham (KS) system of non-interacting electrons as a reference, with all complications buried in the exchange-correlation energy (Exc). The adiabatic connection formula gives…
We find the numerically exact partition potential for 1-D systems of interacting electrons designed to model diatomic molecules. At integer fragment occupations, the kinetic contribution to the partition potential develops sharp features in…
We derive and analyze a hierarchy of approximations to the strongly correlated limit of the Hohenberg-Kohn functional. These "density representability approximations" are obtained by first noting that in the strongly correlated limit,…
A long-standing puzzle in density-functional theory is the issue of the long-range behavior of the Kohn-Sham exchange-correlation potential at metal surfaces. As an important step towards its solution, it is proved here, through a rigurouos…
We present an alternative to the Kohn-Sham formulation of density functional theory for the ground-state properties of strongly interacting electronic systems. The idea is to start from the limit of zero kinetic energy and systematically…
While in principle exact, Kohn-Sham density functional theory -- the workhorse of computational chemistry -- must rely on approximations for the exchange-correlation functional. Despite staggering successes, present-day approximations still…
The near nucleus behavior of the exchange-correlation potential $v_{xc}({\bf r})$ in Hohenberg-Kohn-Sham density functional theory is investigated. It is shown that near the nucleus the linear term of $O(r)$ of the spherically averaged…
Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between…
In the present paper, we report the details of the kinetic energy and angular distributions of the H^{-}, S^{-}/SH^{-} fragment ions produced due to dissociative electron attachment in H_{2}S molecules at resonances peaking at 2.2 eV, 5.2…