Anomalous expansion and phonon damping due to the Co spin-state transition in RCoO_3 with R = La, Pr, Nd and Eu

We present a combined study of the thermal expansion and the thermal conductivity of the perovskite series RCoO_3 with R = La, Nd, Pr and Eu. The well-known spin-state transition in LaCoO_3 is strongly affected by the exchange of the R ions due to their different ionic radii, i.e. chemical pressure. This can be monitored in detail by measurements of the thermal expansion, which is a highly sensitive probe for detecting spin-state transitions. The Co ions in the higher spin state act as additional scattering centers for phonons, therefore suppressing the phonon thermal conductivity. Based on the analysis of the interplay between spin-state transition and heat transport, we present a quantitative model of the thermal conductivity for the entire series. In PrCoO_3, an additional scattering effect is active at low temperatures. This effect arises from the crystal field splitting of the 4f multiplet, which allows for resonant scattering of phonons between the various 4f levels.Comment: 15 pages including 5 figure

Evidence for Multiple Phase Transitions in La_1-xCa_xCoO_3

We report thermal-expansion and specific-heat data of the series La_1-xCa_xCoO_3 for 0 <= x <= 0.3. For x = 0 the thermal-expansion coefficient alpha(T) features a pronounced maximum around T = 50 K caused by a temperature-dependent spin-state transition from a low-spin state (S=0) at low temperatures towards a higher spin state of the Co^3+ ions. The partial substitution of the La^3+ ions by divalent Ca^2+ ions causes drastic changes in the macroscopic properties of LaCoO_3. Around x ~ 0.125 the large maximum in alpha(T) has completely vanished. With further increasing x three different anomalies develop

Temperature dependence of the response of lithium-drifted germanium detectors to gamma rays

Temperature dependence of lithium-drifted germanium detector response to gamma radiatio

Thermal Conductivity, Thermopower, and Figure of Merit of La_{1-x}Sr_xCoO_3

We present a study of the thermal conductivity k and the thermopower S of single crystals of La_{1-x}Sr_xCoO_3 with 0<= x <= 0.3. For all Sr concentrations La_{1-x}Sr_xCoO_3 has rather low k values, whereas S strongly changes as a function of x. We discuss the influence of the temperature- and the doping-induced spin-state transitions of the Co ions on both, S and k. From S, k, and the electrical resistivity rho we derive the thermoelectric figure of merit Z=S^2/(k*rho). For intermediate Sr concentrations we find notably large values of Z indicating that Co-based materials could be promising candidates for thermoelectric cooling.Comment: 7 pages, 5 figures included, submitted to Phys. Rev.

Reliable quantification of 1,2-dihydroxynaphthalene in urine using a conjugated reference compound for calibration.

After environmental and occupational exposure to naphthalene, 1,2-dihydroxynaphthalene (1,2-DHN) was shown to be one major metabolite in human naphthalene metabolism. However, the instability of free 1,2-DHN complicates the reliable determination of this promising biomarker in urine. To solve this stability problem, glucuronide conjugates of 1,2-DHN and the corresponding isotopically labelled D-6-1,2-dihydroxynaphthalene (D-6-1,2-DHN) were synthesised and applied as reference material and internal standard in a gas chromatographic-tandem mass spectrometric (GC-MS/MS) method. The determination of 1- and 2-naphthol (1-MHN, 2-MHN) was included in the procedure to enable a comprehensive assessment of naphthalene metabolism and exposure. The results of the validation showed a high reliability and sensitivity of the method. The detection limits range from 0.05 to 0.16 mu g/L. Precision and repeatability were determined to range from 1.4 to 6.6% for all parameters. The simultaneous determination of 1- and 2-MHN as additional parameters besides 1,2-DHN enables the application of the method for further metabolism and kinetic studies on naphthalene. The use of glucuronide-derivative reference substances and the application of structurally matched isotopic-labelled internal standards for each substance guarantee a reliable quantification of the main naphthalene metabolites 1,2-DHN and 1- and 2-MHN

Spin-State Transition and Metal-Insulator Transition in La1−x_{1-x}Eux_xCoO3_3}

We present a study of the structure, the electric resistivity, the magnetic susceptibility, and the thermal expansion of La$_{1-x}$Eu$_x$CoO$_3$. LaCoO$_3$ shows a temperature-induced spin-state transition around 100 K and a metal-insulator transition around 500 K. Partial substitution of La$^{3+}$ by the smaller Eu$^{3+}$ causes chemical pressure and leads to a drastic increase of the spin gap from about 190 K in LaCoO$_3$ to about 2000 K in EuCoO$_3$, so that the spin-state transition is shifted to much higher temperatures. A combined analysis of thermal expansion and susceptibility gives evidence that the spin-state transition has to be attributed to a population of an intermediate-spin state with orbital order for $x<0.5$ and without orbital order for larger $x$. In contrast to the spin-state transition, the metal-insulator transition is shifted only moderately to higher temperatures with increasing Eu content, showing that the metal-insulator transition occurs independently from the spin-state distribution of the Co$^{3+}$ ions. Around the metal-insulator transition the magnetic susceptibility shows a similar increase for all $x$ and approaches a doping-independent value around 1000 K indicating that well above the metal-insulator transition the same spin state is approached for all $x$.Comment: 10 pages, 6 figure