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Density functional theory for excited states and special symmetries
Author(s) -
Theophilou Andreas K.
Publication year - 1997
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/(sici)1097-461x(1997)61:2<333::aid-qua16>3.0.co;2-c
Subject(s) - subspace topology , excited state , eigenvalues and eigenvectors , density functional theory , atomic orbital , homogeneous space , quantum mechanics , invariant (physics) , slater determinant , physics , group (periodic table) , mathematical physics , wave function , mathematics , mathematical analysis , geometry , electron
For Hamiltonians which are invariant under a group of transformations, one can restrict the search for the energy eigenstates in spaces whose functions transform according to the irreducible representations of the group. However, the construction of a Slater determinant to represent the equivalent noninteracting system of DFT, with the proper transformation properties, is not trivial. Further such a determinant does not always exist. The use of the subspace theory [J. Phys. C 12, 5419 (1979)] developed initially to deal with the density functional theory for excited states overcomes this difficulty and an equivalent system of one‐particle Kohn and Sham equations is derived with nonintegral occupation numbers in the expression of the density. In this article, we derive the explicit form of the subspace density for systems with spherical symmetry. The density does not depend on the Clebsch‐Gordan coefficients, but only on the radial part of the orbitals entering the determinant of the noninteracting state with largest 1. © 1997 John Wiley & Sons, Inc.