title: Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew-Zunger Self-Interaction Corrected Density Functional Theory Calculations.
abstract: 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. 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.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Susi
authors.initials: S
authors.lastname: Lehtola
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.|Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Martin
authors.initials: M
authors.lastname: Head-Gordon
authors.affiliation: Faculty of Physical Sciences, University of Iceland , 107 Reykjavík, Iceland.|Department of Applied Physics, Aalto University School of Science , P.O. Box 11000, FI-00076 Aalto, Espoo, Finland.
authors.forename: Hannes
authors.initials: H
authors.lastname: Jónsson