title: Design of exchange-correlation functionals through the correlation factor approach.
abstract: The correlation factor model is developed in which the spherically averaged exchange-correlation hole of Kohn-Sham theory is factorized into an exchange hole model and a correlation factor. The exchange hole model reproduces the exact exchange energy per particle. The correlation factor is constructed in such a manner that the exchange-correlation energy correctly reduces to exact exchange in the high density and rapidly varying limits. Four different correlation factor models are presented which satisfy varying sets of physical constraints. Three models are free from empirical adjustments to experimental data, while one correlation factor model draws on one empirical parameter. The correlation factor models are derived in detail and the resulting exchange-correlation holes are analyzed. Furthermore, the exchange-correlation energies obtained from the correlation factor models are employed to calculate total energies, atomization energies, and barrier heights. It is shown that accurate, non-empirical functionals can be constructed building on exact exchange. Avenues for further improvements are outlined as well.
authors.affiliation: Département de Chimie, Université de Montréal, C.P. 6128 Succursale A, Montréal, Québec H3C 3J7, Canada.
authors.forename: Jana
authors.initials: J
authors.lastname: Pavlíková Přecechtělová
authors.affiliation: Institut für Chemie, Theoretische Chemie / Quantenchemie, Sekr. C7, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Hilke
authors.initials: H
authors.lastname: Bahmann
authors.affiliation: Institut für Chemie, Theoretische Chemie / Quantenchemie, Sekr. C7, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp
authors.affiliation: Département de Chimie, Université de Montréal, C.P. 6128 Succursale A, Montréal, Québec H3C 3J7, Canada.
authors.forename: Matthias
authors.initials: M
authors.lastname: Ernzerhof