Valence of cerium ions in selected ternary compounds from the system Ce-Rh-Sn

Abstract

Over the last years, intermetallic compounds from the system Ce–Rh–Sn have attracted a considerable attention owing to a rich variety of strongly correlated electron phenomena they exhibit. CeRhSn2, Ce5Rh4Sn10, Ce2Rh3Sn5 and Ce3Rh4Sn13 are magnetically ordered heavy fermion systems [1-5]. Interestingly, for Ce3+xRh4Sn13-x (0.2<x<0.6) no sign of Kondo effect and long range magnetic order was found down to the temperature of 0.4 K [5]. In turn, CeRhSn shows non-Fermi liquid-type thermodynamic and transport properties at low temperatures [6-7] accompanied by an intermediate valence state of the Ce ions. Further, for CeRhSn, CeRhSn2 and CeRh2Sn4 spin fluctuations due to the Rh 4d electrons were also suggested [1,7-8]. The possible coexistence of magnetic phenomena originating from Ce and Rh makes the unequivocal interpretation of experimental data for these compounds very difficult. Consequently, a detailed understanding of the very complex physical properties/behavior requires the use of a broad spectrum of experimental methods, including extended thermodynamic and transport measurements as well as careful investigations of electronic structure. For these systems the full characterization of Ce 4f states in regard to their occupancy, localization in a conduction band and hybridization with the other valence band states is crucial for an unambiguous determination of ground state properties and the low energy excitations. Thus, X-ray absorption spectroscopy (XAS) is here of great use as a bulk probe which is highly sensitive on chemical states of elements. Furthermore, absorption measurements at the Ce LIII edge results in spectra with minimized lifetime broadening, largely unaffected by complicated many-electron final state effects. These spectra can be used to estimate the numbers for the fractional valence of Ce which originates from the strong hybridization between the Ce 4f and the other valence band states related to the valence fluctuation phenomena and/or to the formation of covalent bonds.