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Orbital‐free effective embedding potential: Density‐matrix functional theory case
Author(s) -
Pernal Katarzyna,
Wesolowski Tomasz A.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22016
Subject(s) - wave function , atomic orbital , embedding , physics , electron , quantum mechanics , density functional theory , density matrix , constraint (computer aided design) , quantum , mathematics , geometry , computer science , artificial intelligence
Minimization of the Hohenberg–Kohn total energy functional E HK [ρ] in the presence of the constraint ρ − ρ B ≥ 0, where ρ B is some arbitrarily chosen electron density comprising integer number of electrons is considered. To access better numerical accuracy of approximations to E HK [ρ] in practice, the search for optimal ρ − ρ B is performed using auxiliary quantities such as orbitals of a reference system of non‐interacting electrons [Wesolowski and Warshel, J Phys Chem 1993, 97, 8050] or a wavefunction‐like object corresponding to interacting electrons [Wesolowski, Phys Rev A 2008, 77, 012504]. In both cases, the condition ρ − ρ B ≥ 0 leads to a local potential ( orbital‐free effective embedding potential ) of the same general form if expressed by means of universal density functionals. In this work, it is shown that the same local potential is obtained if the search for optimal ρ − ρ B is performed among one‐particle reduced density matrices. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009