Density Functional Theory Calculations of Core–Electron Binding Energies at the K-Edge of Heavier Elements

Besley, Nicholas A.

Abstract

The capability to determine core–electron binding energies (CEBEs) is vital in the analysis of X-ray photoelectron spectroscopy, and the continued development of light sources has made inner shell spectroscopy of heavier elements increasingly accessible. Density functional theory is widely used to determine CEBEs of lighter elements (boron–fluorine). It is shown that good performance of exchange-correlation functionals for these elements does not necessarily translate to the calculation of CEBEs for the heavier elements from the next row of the periodic table, and in general, larger errors are observed. Two strategies are explored that improve the accuracy of the calculated CEBEs. The first is to apply element and functional dependent energy corrections, and the second is a reparametrization of a short-range corrected functional. This functional is able to reproduce experimental phosphorus and sulfur K-edge CEBEs with an average error of 0.15 eV demonstrating the importance of reducing the self-interaction error associated with the core electrons and represents progress toward a density functional theory calculation that performs equally well for ionization at the K-edge of all elements.

Citation

Besley, N. A. (2021). Density Functional Theory Calculations of Core–Electron Binding Energies at the K-Edge of Heavier Elements. Journal of Chemical Theory and Computation, https://doi.org/10.1021/acs.jctc.1c00171

• Journal Article Type: Article
• Acceptance Date: May 17, 2021
• Online Publication Date: May 27, 2021
• Publication Date: May 27, 2021
• Deposit Date: May 28, 2021
• Publicly Available Date: May 28, 2022
• Journal: Journal of Chemical Theory and Computation
• Print ISSN: 1549-9618
• Electronic ISSN: 1549-9626
• Publisher: American Chemical Society (ACS)
• Peer Reviewed: Peer Reviewed
• DOI: https://doi.org/10.1021/acs.jctc.1c00171
• Keywords: Physical and Theoretical Chemistry; Computer Science Applications
• Public URL: https://nottingham-repository.worktribe.com/output/5576018
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.jctc.1c00171