Symmetry breaking and self-interaction correction in the chromium atom and dimer

Maniar, Rohan; Withanage, Kushantha P. K.; Shahi, Chandra; Kaplan, Aaron D.; Perdew, John P.; Pederson, Mark R.

doi:10.1063/5.0180863

Title: Symmetry breaking and self-interaction correction in the chromium atom and dimer

Journal Article · 07 April 2024 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0180863 · OSTI ID:2472556

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^[2]; Shahi, Chandra ^[1];

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Tulane University, New Orleans, LA (United States)
University of Texas at El Paso, TX (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Density functional approximations to the exchange–correlation energy can often identify strongly correlated systems and estimate their energetics through energy-minimizing symmetry-breaking. In particular, the binding energy curve of the strongly correlated chromium dimer is described qualitatively by the local spin density approximation (LSDA) and almost quantitatively by the Perdew–Burke–Ernzerhof generalized gradient approximation (PBE-GGA), where the symmetry breaking is antiferromagnetic for both. Here, we show that a full Perdew–Zunger self-interaction-correction (SIC) to LSDA seems to go too far by creating an unphysical symmetry-broken state, with effectively zero magnetic moment but non-zero spin density on each atom, which lies ~4 eV below the antiferromagnetic solution. A similar symmetry-breaking, observed in the atom, better corresponds to the 3d↑↑4s↑3d↓↓4s↓ configuration than to the standard 3d↑↑↑↑↑4s↑. For this new solution, the total energy of the dimer at its observed bond length is higher than that of the separated atoms. In conclusion, these results can be regarded as qualitative evidence that the SIC needs to be scaled down in many-electron regions.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; SC0018331

OSTI ID:: 2472556

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 160; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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