| Autor: |
Schwalbe S; Center for Advanced Systems Understanding (CASUS), D-02826 Görlitz, Germany.; Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01328 Dresden, Germany., Schulze WT; Institute for Physical Chemistry, Friedrich Schiller University, D-07743 Jena, Germany., Trepte K; Taiwan Semiconductor Manufacturing Company North America, San Jose, California 95134, United States., Lehtola S; Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of chemical theory and computation [J Chem Theory Comput] 2024 Aug 27; Vol. 20 (16), pp. 7144-7154. Date of Electronic Publication: 2024 Aug 14. |
| DOI: |
10.1021/acs.jctc.4c00694 |
| Abstrakt: |
The Perdew-Zunger (PZ) self-interaction correction (SIC) is an established tool to correct unphysical behavior in density functional approximations. Yet, the PZ-SIC is well-known to sometimes break molecular symmetries. An example of this is the benzene molecule, for which the PZ-SIC predicts a symmetry-broken electron density and molecular geometry, since the method does not describe the two possible Kekulé structures on an even footing, leading to local minima [Lehtola et al. J. Chem. Theory Comput. 2016, 12, 3195]. The PZ-SIC is often implemented with Fermi-Löwdin orbitals (FLOs), yielding the FLO-SIC method, which likewise has issues with symmetry breaking and local minima [Trepte et al. J. Chem. Phys. 2021, 155, 224109]. In this work, we propose a generalization of the PZ-SIC─the ensemble PZ-SIC (E-PZ-SIC) method─which shares the asymptotic computational scaling of the PZ-SIC (albeit with an additional prefactor). The E-PZ-SIC is straightforwardly applicable to various molecules, merely requiring one to average the self-interaction correction over all possible Kekulé structures, in line with chemical intuition. We showcase the implementation of the E-PZ-SIC with FLOs, as the resulting E-FLO-SIC method is easy to realize on top of an existing implementation of the FLO-SIC. We show that the E-FLO-SIC indeed eliminates symmetry breaking, reproducing a symmetric electron density and molecular geometry for benzene. The ensemble approach suggested herein could also be employed within approximate or locally scaled variants of the PZ-SIC and its FLO-SIC versions. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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