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

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

Sonolytic Oxidation of Tc(IV)O2nH2O Nanoparticles to Tc(VII)O4 in Aqueous Solution

Sonolysis of a hydrosol of TcO2nH2O was investigated in the Ar- or He- atmosphere. Colloidal TcO2nH2O nanoparticles were irradiated with a 200 kHz and 1.25 W/cm2 ultrasound. It was found that the TcO2nH2O colloids dispersed in an aqueous solution (under Ar or He atmosphere) was completely dissolved by ultrasonic irradiation (200 kHz, 200 W). The original brownish black color of the suspension slowly disappeared leaving behind a colorless solution. This change suggests that oxidation of Tc(IV) to Tc(VII) takes place. The oxidation was almost complete during 30 minutes sonication time under argon atmosphere for initial concentration of 6.0E-5 M. Addition of t-butyl alcohol, an effective radical scavenger which readily reacts with OH radicals, supressed the dissolution of TcO2nH2O colloids. This reaction indicates that TcO2nH2O molecules are oxidized by OH radicals produced in cavitation bubbles. Received: 20 November 2009; Revised:14 April 2010; Accepted: 18 April 201

Sonolytic Oxidation of Tc(IV)O2nH2O Nanoparticles to Tc(VII)O4 in Aqueous Solution

Sonolysis of a hydrosol of TcO2nH2O was investigated in the Ar- or He- atmosphere. Colloidal TcO2nH2O nanoparticles were irradiated with a 200 kHz and 1.25 W/cm2 ultrasound. It was found that the TcO2nH2O colloids dispersed in an aqueous solution (under Ar or He atmosphere) was completely dissolved by ultrasonic irradiation (200 kHz, 200 W). The original brownish black color of the suspension slowly disappeared leaving behind a colorless solution. This change suggests that oxidation of Tc(IV) to Tc(VII) takes place. The oxidation was almost complete during 30 minutes sonication time under argon atmosphere for initial concentration of 6.0E-5 M. Addition of t-butyl alcohol, an effective radical scavenger which readily reacts with OH radicals, supressed the dissolution of TcO2nH2O colloids. This reaction indicates that TcO2nH2O molecules are oxidized by OH radicals produced in cavitation bubbles. Received: 20 November 2009; Revised:14 April 2010; Accepted: 18 April 201

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

Shock wave equation of state of muscovite

Shock wave data to provide an equation of state of muscovite (initial density: 2.835 g/cm^3) were determined up to a pressure of 141 GPa. The shock velocity (Us) versus particle velocity (Up) data are fit with a single linear relationship: U_s=4.62(±0.12) +1.27(±0.04)U_p (km/s). Third-order Birch-Murnaghan equation of state parameters (isentropic bulk modulus and isentropic pressure derivative of bulk modulus) are K_(os)=52±4GPa and K'_(os)=3.2±0.3. The pressure-temperature relation along the Hugoniot suggests that muscovite may dehydrate to KAlSi_3O_8 (hollandite), corundum, and water, with a small volume change, above 80 GPa. Thermodynamic calculations of the equilibrium pressure for the dehydration yields a significantly lower value. Observed unloading paths from shock pressures up to about 80 GPa are steeper in a density-pressure plane than the Hugoniot and become shallower with increasing shock pressure above that pressure. The changing slope may indicate that devolatilization occurs during unloading above 80 GPa. The present equation of state data for muscovite are compared with results of previously reported recovery experiments

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