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.
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.
We report a polarized neutron diffraction study conducted to reveal the nature of the weak ferromagnetic moment in the superconducting ferromagnet UCoGe. We find that the ordered moment in the normal phase in low magnetic fields (B // c) is predominantly located at the U atom and has a magnitude of about 0.1 muB at 3 T, in agreement with bulk magnetization data. By increasing the magnetic field the U moment grows to about 0.3 muB in 12 T and most remarkably, induces a substantial moment (about 0.2 muB) on the Co atom directed antiparallel to the U moment. The anomalous polarizability of the Co 3d orbitals is unique among uranium intermetallics and might reflect the proximity to a magnetic quantum critical point of UCoGe in zero field.
CaFe2As2 single crystals under uniaxial pressure applied along the c axis exhibit the coexistence of several structural phases at low temperatures. We show that the room-temperature tetragonal phase is stabilized at low temperatures for pressures above 0.06 GPa, and its weight fraction attains a maximum in the region where superconductivity is observed under applied uniaxial pressure. Simultaneous resistivity measurements strongly suggest that this phase is responsible for the superconductivity in CaFe2As2 found below 10 K in samples subjected to nonhydrostatic pressure conditions.
Single crystal neutron and high-energy x-ray diffraction have identified the phase lines corresponding to transitions between the ambient-pressure tetragonal (T), the antiferromagnetic orthorhombic (O) and the non-magnetic collapsed tetragonal (cT) phases of CaFe2As2. We find no evidence of additional structures for pressures up to 2.5 GPa (at 300 K). Both the T-cT and O-cT transitions exhibit significant hysteresis effects and we demonstrate that coexistence of the O and cT phases can occur if a non-hydrostatic component of pressure is present. Measurements of the magnetic diffraction peaks show no change in the magnetic structure or ordered moment as a function of pressure in the O phase and we find no evidence of magnetic ordering in the cT phase. Band structure calculations show that the transition results in a strong decrease of the iron 3d density of states at the Fermi energy, consistent with a loss of the magnetic moment.
