Rigorous definition of oxidation states of ions in solids

TL;DR

This paper introduces a rigorous, wavefunction-based method for defining oxidation states in solids, avoiding traditional charge density approaches and applicable to various extended systems.

Contribution

It presents a novel, topology-based procedure for electron partitioning that redefines oxidation states without relying on charge transfer assumptions.

Findings

Provides a rigorous electrostatic framework for solids

Applicable to films and nanowires

Reformulates oxidation states without charge transfer assumptions

Abstract

We present justification and rigorous procedure for electron partitioning among atoms in extended systems. The method is based on wavefunction topology and the modern theory of polarization, rather than charge density partitioning or wavefunction projection, and, as such, re-formulates the concept of oxidation state without assuming real-space charge transfer between atoms. This formulation provides rigorous electrostatics of finite extent solids, including films and nanowires.