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

• Main Authors: Jackson, K.A (Author), Johnson, J.K (Author), Peralta, J.E (Author), Perdew, J.P (Author), Sharkas, K. (Author), Withanage, K.P.K (Author)
• Format: Article
• Language: English
• Published: American Institute of Physics Inc. 2022
• Subjects: Adsorption; Adsorption energies; Density functional theory; Density-functional-theory; Errors; Local spin density approximation; Metal ions; Molecules; Numerical methods; Orbitals; Perdew-burke-ernzerhof; Self-interaction corrections; Self-interaction error; Self-interactions; Small molecules; Transition metal compounds; Transition metal ions; Transition metals
• Online Access: View Fulltext in Publisher

 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. © 2022 Author(s).