Exact non-additive kinetic potentials in realistic chemical systems

摘要

In methods based on frozen-density embedding theory or subsystem formulation of density functional theory, the non-additive kinetic potential (v _(tn)ad(r)) needs to be approximated. Since v _(tn)ad(r) is defined as a bifunctional, the common strategies rely on approximating v _(tn)ad[ρ _A,ρ _B](r). In this work, the exact potentials (not bifunctionals) are constructed for chemically relevant pairs of electron densities (ρ _A and ρ _B) representing: dissociating molecules, two parts of a molecule linked by a covalent bond, or valence and core electrons. The method used is applicable only for particular case, where ρ _A is a one-electron or spin-compensated two-electron density, for which the analytic relation between the density and potential exists. The sum ρ _A ρ _B is, however, not limited to such restrictions. Kohn-Sham molecular densities are used for this purpose. The constructed potentials are analyzed to identify the properties which must be taken into account when constructing approximations to the corresponding bifunctional. It is comprehensively shown that the full von Weizs?cker component is indispensable in order to approximate adequately the non-additive kinetic potential for such pairs of densities.