Fermi–Löwdin orbital self-interaction correction of adsorption energies on transition metal ions

Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu+, Zn+, Zn2+, and Mn+ in local spin den...

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Bibliographic Details
Published in:The Journal of chemical physics 2022-04, Vol.156 (13), p.134102-134102
Main Authors: Withanage, Kushantha P. K., Sharkas, Kamal, Johnson, J. Karl, Perdew, John P., Peralta, Juan E., Jackson, Koblar A.
Format: Article
Language:English
Subjects:
Adsorption
Approximation
Copper
Density functional theory
Errors
Manganese
Mathematical analysis
Metal ions
Transition metals
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Summary:Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu+, Zn+, Zn2+, and Mn+ in local spin density approximation (LSDA) and Perdew, Burke, Ernzerhof (PBE) generalized gradient approximation calculations compared to reference values computed using the coupled-cluster with single, doubles, and perturbative triple excitations method. These errors are significantly reduced by removing self-interaction using the Perdew–Zunger self-interaction correction (PZ-SIC) in the Fermi–Löwdin Orbital (FLO) SIC framework. In the case of FLO-PBE, typical errors are reduced to less than 0.1 eV. Analysis of the results using DFT energies evaluated on self-interaction-corrected densities [DFT(@FLO)] indicates that the density-driven contributions to the FLO-DFT adsorption energy corrections are roughly the same size in DFT = LSDA and PBE, but the total corrections due to removing self-interaction are larger in LSDA.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0078970