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Title: Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations

Implentation of seminumerical stability analysis for calculations using the Perdew-Zunger self-interaction correction is described. It is shown that real-valued solutions of the Perdew-Zunger equations for gas phase atoms are unstable with respect to imaginary orbital rotations, confirming that a proper implementation of the correction requires complex-valued orbitals. The orbital density dependence of the self-interaction corrected functional is found to lead to multiple local minima in the case of the acrylic acid, H 6, and benzene molecules. Finally, in the case of benzene, symmetry breaking that results in incorrect ground state geometry is found to occur, erroneously leading to alternating bond lengths in the molecule.
Authors:
 [1] ;  [2] ;  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Univ. of Iceland, Reykjavík (Iceland); Aalto Univ., Espoo (Finland). Dept. of Applied Physics
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 12; Journal Issue: 7; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1478340

Lehtola, Susi, Head-Gordon, Martin, and Jónsson, Hannes. Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations. United States: N. p., Web. doi:10.1021/acs.jctc.6b00347.
Lehtola, Susi, Head-Gordon, Martin, & Jónsson, Hannes. Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations. United States. doi:10.1021/acs.jctc.6b00347.
Lehtola, Susi, Head-Gordon, Martin, and Jónsson, Hannes. 2016. "Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations". United States. doi:10.1021/acs.jctc.6b00347. https://www.osti.gov/servlets/purl/1478340.
@article{osti_1478340,
title = {Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger Self-Interaction Corrected Density Functional Theory Calculations},
author = {Lehtola, Susi and Head-Gordon, Martin and Jónsson, Hannes},
abstractNote = {Implentation of seminumerical stability analysis for calculations using the Perdew-Zunger self-interaction correction is described. It is shown that real-valued solutions of the Perdew-Zunger equations for gas phase atoms are unstable with respect to imaginary orbital rotations, confirming that a proper implementation of the correction requires complex-valued orbitals. The orbital density dependence of the self-interaction corrected functional is found to lead to multiple local minima in the case of the acrylic acid, H6, and benzene molecules. Finally, in the case of benzene, symmetry breaking that results in incorrect ground state geometry is found to occur, erroneously leading to alternating bond lengths in the molecule.},
doi = {10.1021/acs.jctc.6b00347},
journal = {Journal of Chemical Theory and Computation},
number = 7,
volume = 12,
place = {United States},
year = {2016},
month = {6}
}