The first order atomic fragment approach-An orbital-free implementation of density functional theory.

An orbital-free implementation of the original Hohenberg-Kohn theorems is presented, making use of the scaling properties from a fictitious Kohn-Sham system, but without reintroducing orbitals. The first order fragment approach does not contain data or parameters that are fitted to the final outcome of the molecular orbital-free calculation and thus represents a parameter-free implementation of orbital-free density functional theory, although it requires the precalculation of atomic data. Consequently, the proposed method is not limited to a specific type of molecule or chemical bonding. The different approximation levels arise from including (first order) or neglecting (zeroth order) the dependency between the potential and the electron density, which in the bifunctional approach are formally treated as independent variables.