Valence Fluctuation in CeMo2Si2C

TL;DR

This study investigates the valence fluctuation of Ce in CeMo₂Si₂C using various experimental techniques, revealing intermediate valence behavior, Fermi-liquid properties, and hybridization effects, contributing to understanding of correlated electron systems.

Contribution

It provides detailed experimental and theoretical analysis of Ce valence fluctuation in CeMo₂Si₂C, highlighting its intermediate valence state and Fermi-liquid behavior, which was not previously characterized.

Findings

Ce ions are in a valence fluctuating state with <ν> ≈ 3.11

No magnetic ordering observed down to 1.8 K

System exhibits Fermi-liquid behavior with γ = 23.4 mJ/mol·K²

Abstract

We report on the valence fluctuation of Ce in CeMo$_{2}$Si$_{2}$C as studied by means of magnetic susceptibility $\chi(T)$, specific heat $C(T)$, electrical resistivity $\rho(T)$ and x-ray absorption spectroscopy. Powder x-ray diffraction revealed that CeMo$_{2}$Si$_{2}$C crystallizes in CeCr$_{2}$Si$_{2}$C-type layered tetragonal crystal structure (space group \textit{P4/mmm}). The unit cell volume of CeMo$_{2}$Si$_{2}$C deviates from the expected lanthanide contraction, indicating non-trivalent state of Ce ions in this compound. The observed weak temperature dependence of the magnetic susceptibility and its low value indicate that Ce ions are in valence fluctuating state. The formal $L_{III}$ Ce valence in CeMo$_{2}$Si$_{2}$C $<$$\widetilde{\nu}$$>$ = 3.11 as determined from x-ray absorption spectroscopy measurement is well bellow the value $<$$\widetilde{\nu}$$> \simeq$ 3.4 in tetravalent Ce compound CeO$_{2}$. The temperature dependence of specific heat does not show any anomaly down to 1.8 K which rules out any magnetic ordering in the system. The Sommerfeld coefficient obtained from the specific heat data is $\gamma$ = 23.4 mJ/mol\,K$^{2}$. The electrical resistivity follows the $T{^2}$ behavior in the low temperature range below 35 K confirming a Fermi liquid behavior. Accordingly both the Kadowaki Wood ratio $A/\gamma^{2}$ and the Sommerfeld Wilson ratio $\chi(0)/\gamma$ are in the range expected for Fermi-liquid systems. In order to get some information on the electronic states, we calculated the band structure within the density functional theory, eventhough this approach is not able to treat 4f electrons accurately. The non-$f$ electron states crossing the Fermi level have mostly Mo 4d character. They provide the states with which the 4f sates are strongly hybridized, leading to the intermediate valent state.