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

doi:10.1063/5.0078970

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

J Chem Phys. 2022 Apr 7;156(13):134102. doi: 10.1063/5.0078970.

Authors

Kushantha P K Withanage¹, Kamal Sharkas², J Karl Johnson³, John P Perdew⁴, Juan E Peralta¹, Koblar A Jackson¹

Affiliations

¹ Department of Physics and Science of Advanced Materials Program, Central Michigan University, Mount Pleasant, Michigan 48859, USA.
² Department of Physics, Central Michigan University, Mount Pleasant, Michigan 48859, USA.
³ Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, USA.
⁴ Department of Physics and Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.

PMID: 35395893
DOI: 10.1063/5.0078970

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.