Organometallic chemistry of diphosphazanes .13. Palladium complexes of unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY'

Unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY' [YY' = O2C12H8 (L(1)), O2C20H12 (L(2)); Y = Ph and Y' = OC6H4Br-4 (L(3)), OC(6)H(4)Me-4 (L(4)), OC(6)H(3)Me(2)-3,5 (L(5)), N(2)C(3)HMe(2)-3,5 (L(6))] react with cis-[PdCl2(COD)] (COD = cycloocta-1,5-diene) giving the chelate complexes of the type cis-[PdCl2{eta(2)-Ph(2)PN(Pr-i)PYY'}] [YY' = O2C12H8 (1), O2C20H12 (2), Y = Ph and Y' = OC6H4Br-4 (3), OC(6)H(4)Me-4 (4), OC(6)H(3)Me(2)-3,5 (5), N(2)C(3)HMe(2)-3,5 (6)]. The P-N bond in 3 and 5 undergoes a facile cleavage in methanol solution to give cis-[PdCl2{eta(1)Ph(2)P(OMe)}{eta(1)-PhP(NHPri)(Y')}] [Y' = OC6H4Br-4 (7), OC(6)H(3)Me(2)-3,5 (8)]. Reactions of Pd-2(dba)(3) . CHCl3 (dba = dibenzylideneacetone) with the diphosphazanes Ph(2)PN(Pr-i)PPhY' [Y' = OC(6)H(4)Me-4 (L(4)), N(2)C(3)HMe(2)-3,5 (L(6)), N2C3H3 (L(7))] in the presence of MeI yields cis-[PdI2{eta(2)-Ph(2)PN(Pr-i)PPhMe}] (9); the P-O or P-N(pyrazolyl) bond of the starting ligands is cleaved and a p-C(Me) bond is formed. An analogous oxidative addition reaction in the presence of Ph(2)PN(Pr-i)PPh(2) (L(8)) yields cis-[PdI(Me)(eta(2)-L(8))] (10) and cis-[PdI2(eta 2-L(8))] (11). The structures of 8 and 9 have been determined by X-ray diffraction. Copyright (C) 1996 Elsevier Science Ltd

Superconducting YBa2Cu3O7-delta thick films on Ba2RETaO6 (RE=Pr, Nd, Eu, and Dy) substrates

Thick films of YBa2Cu3O7-delta fabricated on polycrystalline Ba2RETaO6 (where RE= Pr, Nd, Eu, and Dy) substrates by dip-coating and partial melting techniques are textured and c-axis oriented, showing predominantly (00l) orientation. All the thick films show a superconducting zero resistance transition of 90 K. SEM studies clearly indicate platelike and needlelike grain growth over a wide area of the thick films. The values of the critical current density for these thick films are similar to 10(4) A/cm(2) at 77 K as determined by the nonresonant R.F. absorption method. Various processing conditions that affect the critical current density of thick films are also discussed.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

Pyrochlore ``dynamic spin-ice'' Pr(2)Sn(2)O(7) and monoclinic Pr(2)Ti(2)O(7): A comparative temperature-dependent Raman study

Here we report a temperature-dependent Raman study of the pyrochlore ``dynamic spin-ice'' compound Pr(2)Sn(2)O(7) and compare the results with its non-pyrochlore (monoclinic) counterpart Pr(2)Ti(2)O(7). In addition to phonon modes, we observe two bands associated with electronic Raman scattering involving crystal field transitions in Pr(2)Sn(2)O(7) at similar to 135 and 460 cm(-1) which couple strongly to phonons. Anomalous temperature dependence of phonon frequencies that are observed in Pyrochlore Pr(2)Sn(2)O(7) are absent in monoclinic Pr(2)Ti(2)O(7). This, therefore, confirms that the strong phonon-phonon anharmonic interactions, responsible for the temperature-dependent anomalous behavior of phonons, arise due to the inherent vacant sites in the pyrochlore structure. (C) 2011 Elsevier Inc. All rights reserved.

Ferromagnetic transition and specific heat of Pr(0.6)Sr(0.4)MnO(3)

The critical properties of orthorhombic Pr(0.6)Sr(0.4)MnO(3) single crystals were investigated by a series of static magnetization measurements along the three different crystallographic axes as well as by specific heat measurements. A careful range-of-fitting-analysis of the magnetization and susceptibility data obtained from the modified Arrott plots shows that Pr(0.6)Sr(0.4)MnO(3) has a very narrow critical regime. Nevertheless, the system belongs to the three-dimensional (3D) Heisenberg universality class with short-range exchange. The critical exponents obey Widom scaling and are in excellent agreement with the single scaling equation of state M(H,epsilon) = vertical bar epsilon vertical bar(beta) f(+/-)(H/vertical bar epsilon vertical bar((beta+gamma)); with f(+) for T > T(c) and f(-) for T < T(c). A detailed analysis of the specific heat that account for all relevant contributions allows us to extract and analyze the contribution related to the magnetic phase transition. The specific heat indicates the presence of a linear electronic term at low temperatures and a prominent contribution from crystal field excitations of Pr. A comparison with data from literature for PrMnO(3) shows that a Pr-Mn magnetic exchange is responsible for a sizable shift in the lowest lying excitation.

Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Anderson transitions in Ln1-x Sr x CoO3 (Ln═Pr or Nd)

Electrical conductivity measurements show that Ln1-x Sr x CoO3, (Ln = Pr or Nd) undergoes a non-metal-metal transition when x≈0 3. The d.c. conductivity of compositions with 0prisingly, however, δ seems to increase with increasing temperature. Thermopower measurements show clear evidence for a change in the mechanism of conduction (around 350 K) from variable range hopping to transport at E c. All these transport properties suggest that Co4+ ions in Ln1-x Sr x CoO3 (0

Anomalous magnetism of Pr in PrCoAsO

Detailed magnetization and magneto-transport measurements studies are carried out to unearth the anomalous magnetism of Pr in PrCoAsO compound. The studied PrCoAsO sample is single phase and crystallized in the tetragonal structure with space group P4/nmm in analogy of ZrCuSiAs type compounds. Detailed magnetization measurements showed that Co moments in PrCoAsO exhibit weakly itinerant ferromagnetic Co spins ordering at below 80 K with a small magnetic moments of similar to 0.12 mu B/f.u. High temperatures Curie-Weiss fit, resulted in effective paramagnetic moment mu(eff) (exp) of 5.91 mu(B)/f.u., which can be theoretically assigned to 3d Co (3.88 mu(B)) and 4f Pr (3.58 mu(B)). Further, a positive Curie-Weiss temperature (Theta) of 136 K is seen, indicating predominant ferromagnetic interactions in PrCoAsO. Detailed transport measurements showed that PrCoAsO exhibit metallic behavior and negative magneto-resistance below ferro-magnetically (FM) ordered state. Surprisingly, the situation of PrCoAsO is similar to non magnetic La containing LaCoAsO and strikingly different than that as reported for magnetic Nd, Sm and Gd i.e., (Nd/Sm/Gd)CoAsO. The magnetic behavior of PrCoAsO being closed to LaCoAsO and strikingly different to that of (Nd/Sm/Gd)CoAsO is unusual. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Rare-earth carboxylates, Ln(2)(III)(mu(3)-OH)(C4H4O5)(2)(C4H2O4)]center dot 2H(2)O Ln = Ce, Pr and Nd]: synthesis, structure and properties

A new series of inorganic-organic hybrid framework compounds, Ln(2)(mu(3)-OH)(C4H4O5)(2)(C4H2O4)]center dot 2H(2)O, (Ln = Ce, Pr and Nd), have been prepared employing a hydrothermal method. Malic acid and fumaric acid form part of the structure. The malate units connect the lanthanide centers forming Ln-O-Ln two-dimensional layers, which are cross-linked by the fumarate units forming the three-dimensional structure. Extra framework water molecules form a dimer and occupy the channels. The water molecules can be reversibly adsorbed. The dehydrated structure did not show any differences in framework structure/ connectivity. The presence of lattice water provides a pathway for proton conductivity. Optical studies suggest an up-conversion behavior involving more than one photon for a neodymium compound.

Evaluation of TRMM PR Sampling Error Over a Subtropical Basin Using Bootstrap Technique

Quantitative use of satellite-derived rainfall products for various scientific applications often requires them to be accompanied with an error estimate. Rainfall estimates inferred from low earth orbiting satellites like the Tropical Rainfall Measuring Mission (TRMM) will be subjected to sampling errors of nonnegligible proportions owing to the narrow swath of satellite sensors coupled with a lack of continuous coverage due to infrequent satellite visits. The authors investigate sampling uncertainty of seasonal rainfall estimates from the active sensor of TRMM, namely, Precipitation Radar (PR), based on 11 years of PR 2A25 data product over the Indian subcontinent. In this paper, a statistical bootstrap technique is investigated to estimate the relative sampling errors using the PR data themselves. Results verify power law scaling characteristics of relative sampling errors with respect to space-time scale of measurement. Sampling uncertainty estimates for mean seasonal rainfall were found to exhibit seasonal variations. To give a practical example of the implications of the bootstrap technique, PR relative sampling errors over a subtropical river basin of Mahanadi, India, are examined. Results reveal that the bootstrap technique incurs relative sampling errors < 33% (for the 2 degrees grid), < 36% (for the 1 degrees grid), < 45% (for the 0.5 degrees grid), and < 57% (for the 0.25 degrees grid). With respect to rainfall type, overall sampling uncertainty was found to be dominated by sampling uncertainty due to stratiform rainfall over the basin. The study compares resulting error estimates to those obtained from latin hypercube sampling. Based on this study, the authors conclude that the bootstrap approach can be successfully used for ascertaining relative sampling errors offered by TRMM-like satellites over gauged or ungauged basins lacking in situ validation data. This technique has wider implications for decision making before incorporating microwave orbital data products in basin-scale hydrologic modeling.

Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr, Nd, Sm). II.

We investigate the direct correspondence between Co band ferromagnetism and structural parameters in the pnictide oxides RCoPO for different rare-earth ions (R = La, Pr, Nd, Sm) by means of muon-spin spectroscopy and ab initio calculations, complementing our results published previously G. Prando et al., Common effect of chemical and external pressures on the magnetic properties of RCoPO (R = La, Pr), Phys. Rev. B 87, 064401 (2013)]. We find that both the transition temperature to the ferromagnetic phase T-C and the volume of the crystallographic unit cell V are conveniently tuned by the R ionic radius and/or external pressure. We report a linear correlation between T-C and V and our ab initio calculations unambiguously demonstrate a full equivalence of chemical and external pressures. As such, we show that R ions influence the ferromagnetic phase only via the induced structural shrinkage without involving any active role from the electronic f degrees of freedom, which are only giving a sizable magnetic contribution at much lower temperatures.

Two bifurcation transitions of the floating half zone convection in a fat liquid bridge of larger Pr

The transient process of the thermocapillary convection was obtained for the large Pu floating half zone by using the method of three-dimensional and unsteady numerical simulation. The convection transits directly from steady and axisymmetric state to oscillatory flow for slender liquid bridge, and transits first from steady and axisymmetric convection to the steady and non-axisymmetric convection, then, secondly to the oscillatory convection for the fatter liquid bridge. This result implies that the volume of liquid bridge is not only a sensitive critical parameter for the onset of oscillation, but also relates to the new mechanism for the onset of instability in the floating half zone convection even in case of large Prandtl number fluid.

Proper orthogonal decomposition of oscillatory Marangoni flow in half-zone liquid bridges of low-Pr fluids

Proper orthogonal decomposition (POD) using method of snapshots was performed on three different types of oscillatory Marangoni flows in half-zone liquid bridges of low-Pr fluid (Pr = 0.01). For each oscillation type, a series of characteristic modes (eigenfunctions) have been extracted from the velocity and temperature disturbances, and the POD provided spatial structures of the eigenfunctions, their oscillation frequencies, amplitudes, and phase shifts between them. The present analyses revealed the common features of the characteristic modes for different oscillation modes: four major velocity eigenfunctions captured more than 99% of the velocity fluctuation energy form two pairs, one of which is the most energetic. Different from the velocity disturbance, one of the major temperature eigenfunctions makes the dominant contribution to the temperature fluctuation energy. On the other hand, within the most energetic velocity eigenfuction pair, the two eigenfunctions have similar spatial structures and were tightly coupled to oscillate with the same frequency, and it was determined that the spatial structures and phase shifts of the eigenfunctions produced the different oscillatory disturbances. The interaction of other major modes only enriches the secondary spatio-temporal structures of the oscillatory disturbances. Moreover, the present analyses imply that the oscillatory disturbance, which is hydrodynamic in nature, primarily originates from the interior of the liquid bridge. (C) 2007 Elsevier B.V. All rights reserved.