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

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.

4 pages, 3 figures