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

Kushantha P.K. Withanage, Kamal Sharkas, J. Karl Johnson, John P. Perdew, Juan E. Peralta, Koblar A. Jackson

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Article number134102
JournalJournal of Chemical Physics
Volume156
Issue number13
DOIs
StatePublished - Apr 7 2022

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