Charge-Density-Wave Ordering in the Metal-Insulator Transition Compound PrRu4P12

X-ray and electron diffraction measurements on the metal-insulator (M-I) transition compound PrRu$_4$P$_{12}$ have revealed the emergence of a periodic ordering of charge density around the Pr atoms. It is found that the ordering is associated with the onset of a low temperature insulator phase. These conclusions are supported by the facts that the space group of the crystal structure transforms from Im$\bar{3}$ to Pm$\bar{3}$ below the M-I transition temperature and also that the temperature dependence of the superlattice peaks in the insulator phase follows the squared BCS function. The M-I transition could be originated from the perfect nesting of the Fermi surface and/or the instability of the $f$ electrons.Comment: 4 pages, 5 figures, Phys. Rev. B (2004) (in press

Metal-insulator transition in PrRu4_4P12_{12} and SmRu4_4P12_{12} investigated by optical spectroscopy

Electronic structures of the filled-skutterudite compounds PrRu$_4$P$_{12}$ and SmRu$_4$P$_{12}$, which undergo a metal-insulator transition (MIT) at $T_{\rm MI}$ = 60 K and 16 K, respectively, have been studied by means of optical spectroscopy. Their optical conductivity spectra develop an energy gap of $\sim$ 10 meV below $T_{\rm MI}$. The observed characteristics of the energy gap are qualitatively different from those of the Kondo semiconductors. In addition, optical phonon peaks in the spectra show anomalies upon the MIT, including broadening and shifts at $T_{\rm MI}$ and an appearance of new peaks below $T_{\rm MI}$. These results are discussed in terms of density waves or orbital ordering previously predicted for these compounds.Comment: 4pages, 4figures, submitted to Physical Review

Single Crystal Growth of Skutterudite CoP3 under High Pressure

A new method to grow single crystals of skutterudite compounds is examined. Using a wedge-type, cubic-anvil, high-pressure apparatus, single crystals of CoP3 were grown from stoichiometric melts under a pressure of 3.5 GPa. Powder x-ray diffraction and electron probe microanalysis measurements indicate that the as-grown boules are a single phase of CoP3. The results suggest that CoP3 is a congruent melting compound under high pressure.Comment: 6pages,5 figures, J. Crystal Growth (in press

Anomalous elastic softening of SmRu_{4}P_{12} under high pressure

The filled skutterudite compound SmRu_4P_{12} undergoes a complex evolution from a paramagnetic metal (phase I) to a probable multipolar ordering insulator (phase II) at T_{MI} = 16.5 K, then to a magnetically ordered phase (phase III) at T_{N} = 14 K. Elastic properties under hydrostatic pressures were investigated to study the nature of the ordering phases. We found that distinct elastic softening above T_{MI} is induced by pressure, giving evidence of quadrupole degeneracy of the ground state in the crystalline electric field. It also suggests that quadrupole moment may be one of the order parameters below T_{MI} under pressure. Strangely, the largest degree of softening is found in the transverse elastic constant C_{T} at around 0.5-0.6 GPa, presumably having relevancy to the competing and very different Gruneisen parameters \Omega of T_{MI} and T_{N}. Interplay between the two phase transitions is also verified by the rapid increase of T_{MI} under pressure with a considerably large \Omega of 9. Our results can be understood on the basis of the proposed octupole scenario for SmRu_4P_{12}.Comment: 7 pages, 7 figure

XANES study of rare-earth valency in LRu4P12 (L = Ce and Pr)

Valency of Ce and Pr in LRu4P12 (L = Ce and Pr) was studied by L2,3-edge x-ray absorption near-edge structure (XANES) spectroscopy. The Ce-L3 XANES spectrum suggests that Ce is mainly trivalent, but the 4f state strongly hybridizes with ligand orbitals. The band gap of CeRu4P12 seems to be formed by strong hybridization of 4f electrons. Pr-L2 XANES spectra indicate that Pr exists in trivalent state over a wide range in temperature, 20 < T < 300 K. We find that the metal-insulator (MI) transition at TMI = 60 K in PrRu4P12 does not originate from Pr valence fluctuation.Comment: 4 page

Role of p-f Hybridization in the Metal-Non-Metal Transition of PrRu4P12

Electronic state evolution in the metal-non-metal transition of PrRu4P12 has been studied by X-ray and polarized neutron diffraction experiments. It has been revealed that, in the low-temperature non-metallic phase, two inequivalent crystal-field (CF) schemes of Pr3+ 4f^2 electrons with Gamma_1 and Gamma_4^(2) ground states are located at Pr1 and Pr2 sites forming the bcc unit cell surrounded by the smaller and larger cubic Ru-ion sublattices, respectively. This modulated electronic state can be explained by the p-f hybridization mechanism taking two intermediate states of 4f^1 and 4f^3. The p-f hybridization effect plays an important role for the electronic energy gain in the metal-non-metal transition originated from the Fermi surface nesting.Comment: 5 pages, 5 figures. Accepted by J. Phys. Soc. Jp

Pressure-temperature phase diagram of the heavy-electron superconductor URu2Si2

The pressure-temperature phase diagram of the heavy-electron superconductor URu2Si2 has been reinvestigated by ac-susceptibility and elastic neutron-scattering (NS) measurements performed on a small single-crystalline rod (2 mm in diameter, 6 mm in length) in a Cu-Be clamp-type high-pressure cell (P < 1.1 GPa). At ambient pressure, this sample shows the weakest antiferromagnetic (AF) Bragg reflections reported so far, corresponding to the volume-averaged staggered moment of mord ~ 0.011 mB/U. Under applied pressure, the AF scattering intensity exhibits a sharp increase at P ~ 0.7 GPa at low temperatures. The saturation value of the AF scattering intensity above 0.7 GPa corresponds to mord ~ 0.41 mB/U, which is in good agreement with that (~ 0.39 mB/U) observed above 1.5 GPa in our previous NS measurements. The superconductivity is dramatically suppressed by the evolution of AF phase, indicating that the superconducting state coexists only with the hidden order phase. The presence of parasitic ferro- and/or antiferromagnetic phases with transition temperatures T1star =120(5) K, T2star = 36(3) K and T3star = 16.5(5) K and their relationship to the low-T ordered phases are also discussed.Comment: 6 pages, 7 figures, submitted to J. Magn. Magn. Mater. (ICM2006

31P-NMR and muSR Studies of Filled Skutterudite Compound SmFe4P12: Evidence for Heavy Fermion Behavior with Ferromagnetic Ground State

The 31P-NMR (nuclear magnetic resonance) and muSR (muon spin relaxation) measurements on the filled skutterudite system SmFe4P12 have been carried out. The temperature T dependence of the 31P-NMR spectra indicates the existence of the crystalline electric field effect splitting of the Sm3+$ (J = 5/2) multiplet into a ground state and an excited state of about 70 K. The spin-lattice relaxation rate 1/T1 shows the typical behavior of the Kondo system, i.e., 1/T1 is nearly T independent above 30 K, and varies in proportion to T (the Korringa behavior, 1/T1 \propto T) between 7.5 K and 30 K. The T dependence deviated from the Korringa behavior below 7 K, which is independent of T in the applied magnetic field of 1 kOe, and suppressed strongly in higher fields. The behavior is explained as 1/T1is determined by ferromagnetic fluctuations of the uncovered Sm3+ magnetic moments by conduction electrons. The muSR measurements in zero field show the appearance of a static internal field associated with the ferromagnetic order below 1.6 K.Comment: 6 pages, 9 figures, to be published in J. Phys. Soc. Jpn. 75 (2006

Theory of Metal-Insulator Transition in PrRu4P12 and PrFe4P12

All symmetry allowed couplings between the 4f^2-electron ground state doublet of trivalent praseodymium in PrRu4P12 and PrFe4P12 and displacements of the phosphorus, iron or ruthenium ions are considered. Two types of displacements can change the crystal lattice from body-centred cubic to simple orthorhombic or to simple cubic. The first type lowers the point group symmetry from tetrahedral to orthorhombic, while the second type leaves it unchanged, with corresponding space group reductions Im3 --> Pmmm and Im3 --> Pm3 respectively. In former case, the lower point-group symmetry splits the degeneracy of the 4f^2 doublet into states with opposite quadrupole moment, which then leads to anti-quadrupolar ordering, as in PrFe4P12. Either kind of displacement may conspire with nesting of the Fermi surface to cause the metal-insulator or partial metal-insulator transition observed in PrFe4P12 and PrRu4P12. We investigate this scenario using band-structure calculations, and it is found that displacements of the phosphorus ions in PrRu4P12 (with space group reduction Im3 --> Pm3) open a gap everywhere on the Fermi surface.Comment: 6 page