Intermediate-valence behavior of the transition-metal oxide CaCu$_3$Ru$_4$O$_{12}$

TL;DR

This study investigates CaCu$_3$Ru$_4$O$_{12}$, revealing its intermediate-valence behavior through experimental and theoretical methods, characterized by temperature-dependent susceptibility, structural changes, and electronic state crossover.

Contribution

It provides a comprehensive multi-method analysis confirming CaCu$_3$Ru$_4$O$_{12}$ as a classical intermediate-valence system with charge fluctuations.

Findings

Susceptibility shows a broad maximum around 150-160 K.

Structural volume change occurs without altering the crystal structure.

NMR indicates a crossover from localized to itinerant electronic states.

Abstract

The transition--metal oxide CaCu$_3$Ru$_4$O$_{12}$ with perovskite--type structure shows characteristic properties of an intermediate--valence system. The temperature--dependent susceptibility exhibits a broad maximum around $150 - 160$ K. At this temperature, neutron powder diffraction reveals a small but significant volume change whereby the crystal structure is preserved. Moreover, the temperature--dependent resistivity changes its slope. NMR Knight shift measurements of Ru reveal a cross--over from high temperature paramagnetic behavior of localized moments to itinerant band states at low temperatures. Additional density--functional theory calculations can relate the structural anomaly with the $d$--electron number. The different experimental and calculational methods result in a mutually consistent description of CaCu$_3$Ru$_4$O$_{12}$ as an intermediate--valent system in the classical sense of having low--energy charge fluctuations.