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Title: A well-scaling natural orbital theory

Abstract

Here, we introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree–Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals of the oneparticle density matrix.

Authors:
 [1];  [2];  [3]
  1. The Abdus Salam International Centre for Theoretical Physics (ICTP), Trieste (Italy)
  2. Rutgers Univ., Piscataway, NJ (United States). Dept. of Physics and Astronomy; Princeton Univ., NJ (United States). Dept. of Chemistry
  3. Princeton Univ., NJ (United States). Dept. of Chemistry and Dept. of Physics
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1430121
Grant/Contract Number:  
FG02-05ER46201
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 46; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; electronic structure; correlation; density matrix

Citation Formats

Gebauer, Ralph, Cohen, Morrel H., and Car, Roberto. A well-scaling natural orbital theory. United States: N. p., 2016. Web. doi:10.1073/pnas.1615729113.
Gebauer, Ralph, Cohen, Morrel H., & Car, Roberto. A well-scaling natural orbital theory. United States. doi:10.1073/pnas.1615729113.
Gebauer, Ralph, Cohen, Morrel H., and Car, Roberto. Tue . "A well-scaling natural orbital theory". United States. doi:10.1073/pnas.1615729113. https://www.osti.gov/servlets/purl/1430121.
@article{osti_1430121,
title = {A well-scaling natural orbital theory},
author = {Gebauer, Ralph and Cohen, Morrel H. and Car, Roberto},
abstractNote = {Here, we introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled approximations to the two-particle density matrix that yield algebraic scaling in general, and Hartree–Fock scaling in its seniority-zero version. Results from the latter version for small molecular systems are compared with those of highly accurate quantum-chemical computations. The energies lie above full configuration interaction calculations, close to doubly occupied configuration interaction calculations. Their accuracy is considerably greater than that obtained from current density-functional theory approximations and from current functionals of the oneparticle density matrix.},
doi = {10.1073/pnas.1615729113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 46,
volume = 113,
place = {United States},
year = {Tue Nov 01 00:00:00 EDT 2016},
month = {Tue Nov 01 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 4 works
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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965