Complex orbitals, multiple local minima, and symmetry breaking in perdew-zunger self-interaction corrected density functional theory calculations

Susi Lehtola*, Martin Head-Gordon, Hannes Jónsson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

33 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)3195-3207
Number of pages13
JournalJournal of Chemical Theory and Computation
Volume12
Issue number7
DOIs
Publication statusPublished - 12 Jul 2016

Bibliographical note

Funding Information:
The authors would like to acknowledge the financial support from the Thailand Research Fund (BRG57-80010) and the National Research Council of Thailand-Japan Society for the Promotion of Science (NRCT-JSPS) Joint Research Program. The Royal Golden Jubilee Ph.D. scholarship from Thailand Research Fund and Chulalongkorn University for S. R. is also gratefully acknowledged.

Publisher Copyright:
© 2016 American Chemical Society.

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