Valence Imbalance of Manganese Ions between Surface and Bulk Enhanced by Fermi-Surface Structure in Layered Manganites

TL;DR

This study reveals how Fermi-surface structures influence valence imbalance and Friedel oscillations between surface and bulk in layered manganites, with implications for battery and catalyst technologies.

Contribution

It demonstrates the role of Fermi-surface nesting in surface valence phenomena in layered manganites, extending understanding of surface-bulk electronic differences.

Findings

Surface Mn4+ ions are more abundant than in the bulk.

Friedel oscillations depend on Fermi-surface nesting properties.

Surface valence imbalance is enhanced by better Fermi-surface nesting.

Abstract

To investigate valence imbalance phenomena between the surface and bulk in layered manganites, we analyze an eg-orbital degenerate double-exchange model with surfaces for two types of t2g spin structures. We reconfirm that the surface-induced Friedel oscillations occur in the charged structure and that the number of Mn4+ ions on the surface is larger than that in the bulk. This tendency is found to be more significant, when the eg-electron system has Fermi-surface structures with better nesting properties. The behavior of the Friedel oscillations depends on the nesting properties of the Fermi-surface curves along the direction of the oscillations, and not on the dimension of the system itself. We believe that these results will be useful for the development of high-efficiency cathodes in Li-ion batteries and catalysts.