Complex Orbitals, Multiple Local Minima, and Symmetry Breaking in Perdew-Zunger Self-Interaction Corrected Density Functional Theory Calculations.
- Author(s): Lehtola, Susi
- Head-Gordon, Martin
- Jónsson, Hannes
- et al.
Published Web Locationhttps://doi.org/10.1021/acs.jctc.6b00347
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.