Generalized Pauli constraints in reduced density matrix functional theory

被引:42
作者
Theophilou, Iris [1 ,2 ]
Lathiotakis, Nektarios N. [3 ,4 ]
Marques, Miguel A. L. [5 ]
Helbig, Nicole [1 ,2 ]
机构
[1] Forschungszentrum Julich, Peter Grunberg Inst, D-52425 Julich, Germany
[2] Forschungszentrum Julich, Inst Adv Simulat, D-52425 Julich, Germany
[3] Natl Hellen Res Fnd, Inst Theoret & Phys Chem, GR-11635 Athens, Greece
[4] Max Planck Inst Mikrostrukturphys, D-06120 Halle, Saale, Germany
[5] Univ Halle Wittenberg, Inst Phys, D-06120 Halle, Saale, Germany
关键词
N-REPRESENTABILITY;
D O I
10.1063/1.4918346
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. (C) 2015 AIP Publishing LLC.
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页数:7
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