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Register a new userValence modulations in CeRuSn
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CeRuSn exhibits an extraordinary room temperature structure at 300~K with coexistence of two types of Ce ions, namely trivalent Ce$^{3+}$ and intermediate valent Ce$^{(4-delta)+}$, in a metallic environment. The ordered arrangement of these two Ce types on specific crystallographic sites results in a doubling of the unit cell along the $c$-axis with respect to the basic monoclinic CeCoAl-type structure. Below room temperature, structural modulation transitions with very broad hysteresis have been reported from measurements of various bulk properties. X-ray diffraction revealed that at low temperatures the doubling of the CeCoAl type structure is replaced by a different modulated ground state, approximating a near tripling of the basic CeCoAl cell. The transition is accompanied by a significant contraction of the $c$ axis. We present new x-ray absorption near-edge spectroscopy data at the Ce L$_{3}$ absorption edge, measured on a freshly cleaved surface of a CeRuSn single crystal. In contrast to a previous report, the new data exhibit small but significant variations as function of temperature that are consistent with a transition of a fraction of Ce$^{3+}$ ions to the intermediate valence state, analogous to the $gamma rightarrow alpha$ transition in elemental cerium, when cooling through the structural transitions of CeRuSn. Such results in a valence-modulated state.
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At ambient temperatures, CeRuSn exhibits an extraordinary structure with a coexistence of two types of Ce ions in a metallic environment, namely trivalent Ce3+ and intermediate valent Ce(4-x)+. Charge ordering produces a doubling of the unit cell along the c-axis with respect to the basic monoclinic CeCoAl type structure. Below room temperature, a phase transition with very broad hysteresis has been observed in various bulk properties like electrical resistivity, magnetic susceptibility, and specific heat. The present x-ray diffraction results show that at low temperatures the doubling of the CeCoAl type structure is replaced by an ill-defined modulated ground state. In this state, at least three different modulation periods compete, with the dominant mode close to a tripling of the basic cell. The transition is accompanied by a significant contraction of the c axis. XANES data suggest that the average Ce valence remains constant, thus the observed c axis contraction is not due to any valence transition. We propose a qualitative structure model with modified stacking sequences of Ce3+ and Ce(4-x)+ layers in the various modulated phases. Surprisingly, far below 100 K the modulated state is sensitive to x-ray irradiation at photon fluxes available at a synchrotron. With photon fluxes of order 10E12/s, the modulated ground state can be destroyed on a timescale of minutes and the doubling of the CeCoAl cell observed at room temperature is recovered. The final state is metastable at 10 K. Heating the sample above 60 K again leads to a recovery of the modulated state. Thus, CeRuSn exhibits both thermally and x-ray induced reversible transformations of the Ce3+/Ce(4-x)+ charge ordering pattern. Such a behavior is unique among any know intermetallic compound.
We report on the spin densities in CeRuSn determined at elevated and at low temperatures using polarized neutron diffraction. At 285 K, where the CeRuSn crystal structure, commensurate with the CeCoAl type, contains two different crystallographic Ce sites, we observe that one Ce site is clearly more susceptible to the applied magnetic field whereas the other is hardly polarizable. This finding clearly documents that distnictly different local environment of the two Ce sites causes the Ce ions to split into magnetic Ce3+ and non-magnetic Ce(4-delta)+ valence states. With lowering the temperature, the crystal structure transforms to a structure incommensurately modulated along the c axis. This leads to new inequivalent crystallographic Ce sites resulting in a re-distribution of spin densities. Our analysis using the simplest structural approximant shows that in this metallic system Ce ions co-exist in different valence states. Localized 4f states that fulfill the third Hunds rule are found to be close to the ideal Ce3+ state (at sites with the largest Ce-Ru interatomic distances) whereas Ce(4-delta)+ valence states are found to be itinerant and situated at Ce sites with much shorter Ce-Ru distances. The similarity to the famous alpha-gamma transition in elemental cerium is discussed.
The intermediate valent systems TmSe and SmB6 have been investigated up to 16 and 18 GPa by ac microcalorimetry with a pressure (p) tuning realized in situ at low temperature. For TmSe, the transition from an antiferromagnetic insulator for p<3 GPa to an antiferromagnetic metal at higher pressure has been confirmed. A drastic change in the p variation of the Neel temperature (Tn) is observed at 3 GPa. In the metallic phase (p>3 GPa), Tn is found to increase linearly with p. A similar linear p increase of Tn is observed for the quasitrivalent compound TmS which is at ambiant pressure equivalent to TmSe at p=7 GPa. In the case of SmB6 long range magnetism has been detected above p=8 GPa, i.e. at a pressure slightly higher than the pressure of the insulator to metal transition. However a homogeneous magnetic phase occurs only above 10 GPa. The magnetic and electronic properties are related to the renormalization of the 4f wavefunction either to the divalent or the trivalent configurations. As observed in SmS, long range magnetism in SmB6 occurs already far below the pressure where a trivalent Sm3+ state will be reached. It seems possible, to describe roughly the physical properties of the intermediate valence equilibrium by assuming formulas for the Kondo lattice temperature depending on the valence configuration. Comparison is also made with the appearance of long range magnetism in cerium and ytterbium heavy fermion compounds.
The ternary stannide CeRuSn is a static mixed-valent cerium compound with an or-dering of trivalent and intermediate-valent cerium on two distinct crystallographic sites. 119Sn Mossbauer spectra showed two electronically almost identical tin atoms at 323 K, while at 298 K and below (77 and 4.2 K) two tin sites can clearly be distinguished. 119Sn solid state NMR experiments are performed to probe the local hyperfine fields at the two different Sn sites. 119Sn NMR powder spectra are nicely fitted with two Sn sites with nearly the same magnetic anisotropy, but with different absolute shift values. Both Sn sites are strongly affected by crossover-like transitions between 100 and 280 K. This local-site study confirms the superstructure modulations found in previous investiga-tions. Towards lower temperatures the powder spectra are broadened giving strong evidence for the antiferromagnetically ordered ground state.
The term hidden order refers to an as yet unidentified form of broken-symmetry order parameter that is presumed to exist in the strongly correlated electron system URu2Si2 on the basis of the reported similarity of the heat capacity at its phase transition at To~17 K to that produced by Bardeen-Cooper-Schrieffer (BCS) mean field theory. Here we show that the phase boundary in URu2Si2 has the elliptical form expected for an entropy-driven phase transition, as has been shown to accompany a change in valence. We show one characteristic feature of such a transition is that the ratio of the critical magnetic field to the critical temperature is defined solely in terms of the effective quasiparticle g-factor, which we find to be in quantitative agreement with prior g-factor measurements. We further find the anomaly in the heat capacity at To to be significantly sharper than a BCS phase transition, and, once quasiparticle excitations across the hybridization gap are taken into consideration, loses its resemblance to a second order phase transition. Our findings imply that a change in valence dominates the thermodynamics of the phase boundary in URu2Si2, and eclipses any significant contribution to the thermodynamics from a hidden order parameter.
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