Issue 39, 2020

Limitations of the equivalent core model for understanding core-level spectroscopies

Abstract

The equivalent core model, or the Z + 1 approximation, has been used to interpret the binding energy, BE, shifts observed in X-ray photoelectron spectroscopy, XPS; in particular to relate these shifts to their origin in the electronic structure of the system. Indeed, a recent paper has claimed that the equivalent core model provides an intuitive chemical view of XPS BE shifts. In the present paper, we present a detailed comparison of the electronic structure provided from rigorous core-hole theory and from the equivalent core model to assess the validity and the utility of the use of the equivalent core model. This comparison shows that the equivalent core model provides a qualitative view of the different properties of initial and core-hole electronic structure. It is also shown that a very serious limitation of the equivalent core model is that it fails to distinguish between initial and final state contributions to the shifts of BEs which seriously reduces the utility of the information obtained with the equivalent core model. Indeed, there is a danger of making an incorrect assignment of the importance of relaxation because the equivalent core model appears to stress the role of final state effects. Given the importance of the distinction of initial and final state effects, we provide rigorous definitions of these two effects and we discuss an example where an incorrect interpretation was made based on the use of the equivalent core model.

Graphical abstract: Limitations of the equivalent core model for understanding core-level spectroscopies

Article information

Article type
Paper
Submitted
03 Jul 2020
Accepted
23 Sep 2020
First published
25 Sep 2020

Phys. Chem. Chem. Phys., 2020,22, 22617-22626

Author version available

Limitations of the equivalent core model for understanding core-level spectroscopies

P. S. Bagus, C. Sousa and F. Illas, Phys. Chem. Chem. Phys., 2020, 22, 22617 DOI: 10.1039/D0CP03569F

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