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Local reduced-density-matrix-functional theory: Incorporating static correlation effects in Kohn-Sham equations

Lathiotakis, N.N.; Helbig, N.; Rubio, A.; Gidopoulos, N.I.

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Authors

N.N. Lathiotakis

N. Helbig

A. Rubio



Abstract

We propose a scheme to bring reduced-density-matrix-functional theory into the realm of density functional theory (DFT) that preserves the accurate density functional description at equilibrium, while incorporating accurately static and left-right correlation effects in molecules and keeping the good computational performance of DFT-based schemes. The key ingredient is to relax the requirement that the local potential is the functional derivative of the energy with respect to the density. Instead, we propose to restrict the search for the approximate natural orbitals within a domain where these orbitals are eigenfunctions of a single-particle Hamiltonian with a local effective potential. In this way, fractional natural occupation numbers are accommodated into Kohn-Sham equations allowing for the description of molecular dissociation without breaking spin symmetry. Additionally, our scheme provides a natural way to connect an energy eigenvalue spectrum to the approximate natural orbitals and this spectrum is found to represent accurately the ionization potentials of atoms and small molecules.

Citation

Lathiotakis, N., Helbig, N., Rubio, A., & Gidopoulos, N. (2014). Local reduced-density-matrix-functional theory: Incorporating static correlation effects in Kohn-Sham equations. Physical Review A, 90(3), Article 032511. https://doi.org/10.1103/physreva.90.032511

Journal Article Type Article
Acceptance Date Apr 28, 2014
Online Publication Date Sep 24, 2014
Publication Date Sep 24, 2014
Deposit Date Sep 26, 2014
Publicly Available Date Oct 2, 2014
Journal Physical Review A
Print ISSN 1050-2947
Electronic ISSN 1094-1622
Publisher American Physical Society
Peer Reviewed Peer Reviewed
Volume 90
Issue 3
Article Number 032511
DOI https://doi.org/10.1103/physreva.90.032511
Related Public URLs http://arxiv.org/abs/1407.7128

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Copyright Statement
Reprinted with permission from the American Physical Society: Physical Review A 90, 032511 © 2014 by the American Physical Society. Readers may view, browse, and/or download material for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modified, adapted, performed, displayed, published, or sold in whole or part, without prior written permission from the American Physical Society.






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