Δ‐SCF calculations of core electron binding energies in first‐row transition metal atoms

2022/01/17 by Jason V. Jorstad, Tian Xie, Christine M. Morales +1
Physics and Astronomy · Materials Science · #Advanced Chemical Physics Studies #X-ray Diffraction in Crystallography #Electron and X-Ray Spectroscopy Techniques

paper · doi:10.1002/qua.26881

Abstract

Abstract Core electron binding energies (CEBE) of nickel and copper atoms have been calculated using single‐configuration energy differences, the so‐called Δ‐self‐consistent field (Δ‐SCF) method. Basis set convergence has been examined for calculated L‐shell and M‐shell core electron binding energies, and a wide array of density functionals have been evaluated. Scalar relativistic corrections have been estimated using the popular Douglas‐Kroll‐Hess (DKH) approximation. While basis set convergence and functional dependence mirror the behavior reported in the literature for main group elements, the simplest Δ‐SCF calculations with pure Hartree‐Fock (HF) exchange and no correlation surprisingly outperform all density functionals in reproducing free‐atom CEBE values for Ni and Cu.

Citations

• NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations

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