Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger SelfInteraction Corrected Density Functional Theory Calculations
Implentation of seminumerical stability analysis for calculations using the PerdewZunger selfinteraction correction is described. It is shown that realvalued solutions of the PerdewZunger equations for gas phase atoms are unstable with respect to imaginary orbital rotations, confirming that a proper implementation of the correction requires complexvalued orbitals. The orbital density dependence of the selfinteraction 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]}
 Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
 Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
 Univ. of Iceland, Reykjavík (Iceland); Aalto Univ., Espoo (Finland). Dept. of Applied Physics
 Publication Date:
 Grant/Contract Number:
 AC0205CH11231
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 12; Journal Issue: 7; Journal ID: ISSN 15499618
 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) (SC22)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
 OSTI Identifier:
 1478340
Lehtola, Susi, HeadGordon, Martin, and Jónsson, Hannes. Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger SelfInteraction Corrected Density Functional Theory Calculations. United States: N. p.,
Web. doi:10.1021/acs.jctc.6b00347.
Lehtola, Susi, HeadGordon, Martin, & Jónsson, Hannes. Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger SelfInteraction Corrected Density Functional Theory Calculations. United States. doi:10.1021/acs.jctc.6b00347.
Lehtola, Susi, HeadGordon, Martin, and Jónsson, Hannes. 2016.
"Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew–Zunger SelfInteraction 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 SelfInteraction Corrected Density Functional Theory Calculations},
author = {Lehtola, Susi and HeadGordon, Martin and Jónsson, Hannes},
abstractNote = {Implentation of seminumerical stability analysis for calculations using the PerdewZunger selfinteraction correction is described. It is shown that realvalued solutions of the PerdewZunger equations for gas phase atoms are unstable with respect to imaginary orbital rotations, confirming that a proper implementation of the correction requires complexvalued orbitals. The orbital density dependence of the selfinteraction 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}
}