Exact non-additive kinetic potentials in realistic chemical systems

Piotr de Silva, Tomasz A. Wesolowski

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Abstract

In methods based on frozen-density embedding theory or subsystem formulation of density functional theory, the non-additive kinetic potential (upsilon(nad)(t)(r)) needs to be approximated. Since upsilon(nad)(t)(r) is defined as a bifunctional, the common strategies rely on approximating upsilon(nad)(t)[rho(A), rho(B)](r). In this work, the exact potentials (not bifunctionals) are constructed for chemically relevant pairs of electron densities (rho(A) and rho(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 rho(A) is a one-electron or spin-compensated two-electron density, for which the analytic relation between the density and potential exists. The sum rho(A) + rho(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 Weizsacker component is indispensable in order to approximate adequately the non-additive kinetic potential for such pairs of densities. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4749573]
Original languageEnglish
Article number094110
JournalJournal of Chemical Physics
Volume137
Issue number9
Number of pages13
ISSN0021-9606
DOIs
Publication statusPublished - 2012
Externally publishedYes

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