title: Density-functional theory with effective potential expressed as a direct mapping of the external potential: applications to atomization energies and ionization potentials.
abstract: In this paper the authors further develop and apply the direct-mapping density functional theory to calculations of the atomization energies and ionization potentials. Single-particle orbitals are determined by solving the Kohn-Sham [Phys. Rev. A. 140, 1133 (1965)] equations with a local effective potential expressed in terms of the external potential. A two-parametric form of the effective potential for molecules is proposed and equations for optimization of the parameters are derived using the exchange-only approximation. Orbital-dependent correlation functional is derived from the second-order perturbation theory in its Moller-Plesset-type zeroth-order approximation based on the Kohn-Sham orbitals and orbital energies. The total atomization energies and ionization potentials computed with the second-order perturbation theory were found to be in agreement with experimental values and benchmark results obtained with ab initio wave mechanics methods.
authors.affiliation: Department of Physics, National University of Dnepropetrovsk, Dnepropetrovsk 49050, per Nauchny 13, Ukraine. v_n_glushkov@yahoo.com
authors.forename: Vitaly N
authors.initials: VN
authors.lastname: Glushkov
authors.forename: Sergey I
authors.initials: SI
authors.lastname: Fesenko