Generalized Pauli constraints in reduced density matrix functional theory

Functionals of the one-body reduced density matrix (1-RDM) are routinely minimized under Coleman's ensemble N-representability conditions. Recently, the topic of pure-state N-representability conditions, also known as generalized Pauli constraints, received increased attention following the dis...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-04, Vol.142 (15), p.154108-154108
Main Authors: Theophilou, Iris, Lathiotakis, Nektarios N, Marques, Miguel A L, Helbig, Nicole
Format: Article
Language:English
Subjects:
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
COMPARATIVE EVALUATIONS
Density
DENSITY MATRIX
ELECTRON CORRELATION
ELECTRONS
FUNCTIONALS
HILBERT SPACE
LIMITING VALUES
MINIMIZATION
Optimization
PAULI PRINCIPLE
POTENTIALS
PURE STATES
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Summary:Functionals of the one-body reduced density matrix (1-RDM) are routinely minimized under Coleman's ensemble N-representability conditions. Recently, the topic of pure-state N-representability conditions, also known as generalized Pauli constraints, received increased attention following the discovery of a systematic way to derive them for any number of electrons and any finite dimensionality of the Hilbert space. The target of this work is to assess the potential impact of the enforcement of the pure-state conditions on the results of reduced density-matrix functional theory calculations. In particular, we examine whether the standard minimization of typical 1-RDM functionals under the ensemble N-representability conditions violates the pure-state conditions for prototype 3-electron systems. We also enforce the pure-state conditions, in addition to the ensemble ones, for the same systems and functionals and compare the correlation energies and optimal occupation numbers with those obtained by the enforcement of the ensemble conditions alone.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4918346