PdGa intermetallic hydrogenation catalyst: an NMR and physical property study.

The PdGa intermetallic compound is a highly selective and stable heterogeneous hydrogenation catalyst for the semi-hydrogenation of acetylene. We have studied single crystals of PdGa grown by the Czochralski technique. The (69)Ga electric-field-gradient (EFG) tensor was determined by means of NMR spectroscopy, giving experimental confirmation of both the recently refined structural model of PdGa and the theoretically predicted Pd-Ga covalent bonding scheme. The hydrogenation experiment has detected no hydrogen uptake in the PdGa, thus preventing in situ hydride formation that leads to a reduction of the catalytic selectivity. We have also determined bulk physical properties (the magnetic susceptibility, the electrical resistivity, the thermoelectric power, the Hall coefficient, the thermal conductivity and the specific heat) of single-crystalline PdGa. The results show that PdGa is a diamagnet with metallic electrical resistivity and moderately high thermal conductivity. The thermoelectric power is negative with complicated temperature dependence, whereas the Hall coefficient is positive and temperature-dependent, indicating complexity of the Fermi surface. Partial fulfillment of the NMR Korringa relation reveals that the charge carriers are weakly correlated. Specific heat measurements show that the density of electronic states (DOS) at the Fermi energy of PdGa is reduced to 15% of the DOS of the elemental Pd metal.

The hydrogen dynamics of CsH5(PO4)2 studied by means of nuclear magnetic resonance.

We have investigated the hydrogen dynamics of cesium pentahydrogen diphosphate, CsH(5)(PO(4))(2), by means of nuclear magnetic resonance (NMR) spectroscopy, in order to address the question of why there is no superprotonic phase transition in this compound, in contrast to other structurally similar hydrogen-bonded ionic salts, where a superprotonic transition is frequently found to be present. The analysis of the NMR spectrum and the spin-lattice relaxation rate revealed that the temperature-dependent hydrogen dynamics of CsH(5)(PO(4))(2) involves motional processes (the intra-H-bond jumps and the inter-H-bond jumps at elevated temperatures, as a mechanism of the ionic conductivity) identical to those for the other H-bonded superprotonic salts. The considerably stronger H-bond network in CsH(5)(PO(4))(2) prompts the search for a higher superprotonic transition temperature. However, due to the relatively weak bonding between the {[H(2)PO(4)]}∞ planes in the [100] direction of the CsH(5)(PO(4))(2) structure by means of the ionic bonding via the cesium atoms and the small number of H bonds in that direction (where out of five H bonds in the unit cell, four are directed within the {[H(2)PO(4)]}∞ planes and only one is between the planes), the bonds between the planes become thermally broken and the crystal melts before the H-bond network rearranges via water release into an open structure typical of the superprotonic phase. Were the coupling between the {[H(2)PO(4)]}∞ planes in the CsH(5)(PO(4))(2) somewhat stronger, the superprotonic transition would occur in the same manner as it does in other structurally related hydrogen-bonded ionic salts.

Geometric origin of magnetic frustration in the µ-Al4Mn giant-unit-cell complex intermetallic.

The structurally ordered µ-Al(4)Mn complex intermetallic phase with 563 atoms in the giant unit cell shows the typical broken-ergodicity phenomena of a magnetically frustrated spin system. The low-field zero-field-cooled and field-cooled magnetic susceptibilities show splitting below the spin freezing temperature T(f) = 2.7 K. The ac susceptibility exhibits a frequency-dependent cusp, associated with a frequency-dependent freezing temperature T(f)(ν). The decay of the thermoremnant magnetization is logarithmically slow in time and shows a dependence on the aging time t(w) and the cooling field H(fc) typical of an ultraslow out-of-equilibrium dynamics of a nonergodic spin system that approaches thermal equilibrium, but can never reach it on the experimentally accessible time scale. The above features classify the µ-Al(4)Mn complex intermettalic among spin glasses. The origin of frustration of magnetic interactions was found to be geometrical due to the distribution of a significant fraction of Mn spins on triangles with antiferromagnetic coupling. The µ-Al(4)Mn phase is a geometrically frustrated spin glass.

Dynamical properties and instability of local fluorite BaF(2) structure around doped Mn(2+) ions-EPR and electron spin echo studies.

The electron paramagnetic resonance (EPR) and electron spin echo (ESE) were measured at the X-band for Mn(2+) in a BaF(2) crystal in the temperature range 4.2-300 K. In addition to the cubic symmetry centre, two other lower concentration tetragonal centres were identified. Temperature variations and computer simulation of the EPR spectrum confirm that the cubic symmetry of the MnF(8) centre is deformed to two T(d) tetrahedra of different dimensions at around 45 K. Electron spin relaxation was measured in the temperature range 4.2-35 K, where the ESE signal was detectable. For higher temperature the Mn(2+) dynamics produces homogeneously broadened EPR lines. At the lowest temperatures the spin-lattice relaxation is governed by ordinary phonon processes with 1/T(1)∼T(5). The efficiency of these processes rapidly decreases and at about 11 K a local mode of energy 17 cm(-1) becomes the relaxation mechanism. Phase relaxation observed as ESE signal dephasing indicates that after the local deformation jumps (tunnelling with frequency 4 × 10(8) s(-1)) between the two tetrahedral configurations appear, with the energy barrier being the local mode energy. This motion is directly visible as a resonance-type enhancement of the ESE dephasing rate 1/T(M) around 11 K. Only the cubic centre displays the above dynamics.