Kinetic and Exchange Energy Densities near the Nucleus

We investigate the behavior of the kinetic and the exchange energy densities near the nuclear cusp of atomic systems. Considering hydrogenic orbitals, we derive analytical expressions near the nucleus, for single shells, as well as in the semiclassical limit of large non-relativistic neutral atoms. We show that a model based on the helium iso-electronic series is very accurate, as also confirmed by numerical calculations on real atoms up to two thousands electrons. Based on this model, we propose non-local density-dependent ingredients that are suitable for the description of the kinetic and exchange energy densities in the region close to the nucleus. These non-local ingredients are invariant under the uniform scaling of the density, and they can be used in the construction of non-local exchange-correlation and kinetic functionals.Comment: 11 pages, 7 figure

The interaction-strength interpolation method for main-group chemistry: benchmarking, limitations, and perspectives

We have tested the original interaction-strength-interpolation (ISI) exchange-correlation functional for main group chemistry. The ISI functional is based on an interpolation between the weak and strong coupling limits and includes exact-exchange as well as the G\"orling-Levy second-order energy. We have analyzed in detail the basis-set dependence of the ISI functional, its dependence on the ground-state orbitals, and the influence of the size-consistency problem. We show and explain some of the expected limitations of the ISI functional (i.e. for atomization energies), but also unexpected results, such as the good performance for the interaction energy of dispersion-bonded complexes when the ISI correlation is used as a correction to Hartree-Fock.Comment: 20 pages, 20 figure

Semilocal density functional theory with correct surface asymptotics

Semilocal density functional theory is the most used computational method for electronic structure calculations in theoretical solid-state physics and quantum chemistry of large systems, providing good accuracy with a very attractive computational cost. Nevertheless, because of the non-locality of the exchange-correlation hole outside a metal surface, it was always considered inappropriate to describe the correct surface asymptotics. Here, we derive, within the semilocal density functional theory formalism, an exact condition for the image-like surface asymptotics of both the exchange-correlation energy per particle and potential. We show that this condition can be easily incorporated into a practical computational tool, at the simple meta-generalized-gradient approximation level of theory. Using this tool, we also show that the Airy-gas model exhibits asymptotic properties that are closely related to the ones at metal surfaces. This result highlights the relevance of the linear effective potential model to the metal surface asymptotics.Comment: 6 pages, 4 figure

Semiclassical atom theory applied to solid-state physics

Using the semiclassical neutral atom theory, we extend to fourth order the modified gradient expansion of the exchange energy of density functional theory. This expansion can be applied both to large atoms and solid-state problems. Moreover, we show that it can be employed to construct a simple and non-empirical generalized gradient approximation (GGA) exchange-correlation functional competitive with state-of-the-art GGAs for solids, but also reasonably accurate for large atoms and ordinary chemistry.Comment: 10 pages, 7 figure