Oxidation states and ionicity

Journal article

Walsh, A., Sokol, A.A., Buckeridge, J., Scanlon, D.O. and Catlow, C.R.A. (2018). Oxidation states and ionicity. Nature Materials. 17, p. 958–964. https://doi.org/10.1038/s41563-018-0165-7
AuthorsWalsh, A., Sokol, A.A., Buckeridge, J., Scanlon, D.O. and Catlow, C.R.A.
Abstract

The concepts of oxidation state and atomic charge are entangled in modern materials science. We distinguish between these quantities and consider their fundamental limitations and utility for understanding material properties. We discuss the nature of bonding between atoms and the techniques that have been developed for partitioning electron density. While formal oxidation states help us count electrons (in ions, bonds, lone pairs), variously defined atomic charges are usefully employed in the description of physical processes including dielectric response and electronic spectroscopies. Such partial charges are introduced as quantitative measures in simple mechanistic models of a more complex reality, and therefore may not be comparable or transferable. In contrast, oxidation states are defined to be universal, with deviations constituting exciting challenges as evidenced in mixed-valence compounds, electrides and highly correlated systems. This Perspective covers how these concepts have evolved in recent years, our current understanding and their significance.

Year2018
JournalNature Materials
Journal citation17, p. 958–964
Digital Object Identifier (DOI)https://doi.org/10.1038/s41563-018-0165-7
Web address (URL)https://www.nature.com/articles/s41563-018-0165-7
Publication dates
PrintNov 2018
Online01 Oct 2018
Publication process dates
Accepted14 Mar 2018
Deposited22 Oct 2019
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Buckeridge et al. Reply:
Buckeridge, J., Catlow, C. R. A., Scanlon, D. O., Keal, T. W., Sherwood, P., Miskufova, M., Walsh, A., Woodley, S. M. and Sokol, A. A. (2015). Buckeridge et al. Reply: Physical Review Letters. 115 (2), p. 029702. https://doi.org/10.1103/PhysRevLett.115.029702
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