Lattice charge models and core level shifts in disordered alloys

TL;DR

This paper develops a generalized lattice charge model to analyze core level shifts in disordered alloys, deriving analytical expressions for physical quantities and revealing how charge screening and disorder broadening depend on alloy composition.

Contribution

It extends the charge-excess functional model to multi-species alloys, providing analytical tools for understanding charge distribution and core level shifts.

Findings

Model generalizes linear charge model to multiple species.

Screening becomes more universal with stronger local interactions.

Disorder broadening peaks at specific alloy compositions.

Abstract

Differences in core level binding energies between atoms belonging to the same chemical species can be related to differences in their intra- and extra-atomic charge distributions, and differences in how their core holes are screened. With this in mind, we consider the charge-excess functional model (CEFM) for net atomic charges in alloys [E. Bruno et al., Phys. Rev. Lett. 91, 166401 (2003)]. We begin by deriving the CEFM energy function in order to elucidate the approximations which underpin this model. We thereafter consider the particular case of the CEFM in which the strength of the `local interactions' within all atoms are the same. We show that for binary alloys the ground state charges of this model can be expressed in terms of charge transfer between all pairs of unlike atoms analogously to the linear charge model [R. Magri et al., Phys. Rev. B 42, 11388 (1990)]. Hence the model considered is a generalization of the linear charge model for alloys containing more than two chemical species. We then determine the model's unknown `geometric factors' over a wide range of parameter space. These quantities are linked to the nature of charge screening in the model, and we illustrate that the screening becomes increasingly universal as the strength of the local interactions is increased. We then use the model to derive analytical expressions for various physical quantities, including the Madelung energy and the disorder broadening in the core level binding energies. These expressions are applied to ternary random alloys, for which it is shown that the Madelung energy and magnitude of disorder broadening are maximized at the composition at which the two species with the largest `electronegativity difference' are equal, while the remaining species having a vanishing concentration. This result is somewhat counterintuitive with regards to the disorder broadening since it does not...