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Abstract: We have studied the magnetic and electronic properties of (Ga,Mn)As ferromagnetic semiconductor layers containing low concentrations of room temperature magnetic MnAs precipitates, using x-ray magnetic circular dichroism in x-ray absorption spectroscopy. Measurements below and above the Curie temperature of the (Ga,Mn)As show localized multiplet structures and broad metallic-like line shapes, respectively. By applying magnetic fields below the coercivity of the (Ga,Mn)As layer, the magnetization reversal behavior of the ferromagnetic semiconductor and the MnAs precipitates can be resolved and are found to be independent of each other.
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Jul 2007
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Abstract: We have studied the superconducting properties of sputtered bilayer thin films of Nb and Pd. The superconducting proximity effect suppresses the critical temperature TC of these bilayer systems. Here, we report that this suppression shows a marked layer-sequence dependence: the suppression is larger for a Nb layer capped with Pd rather than buffered by it. We interpret our data in terms of a theoretical model of the proximity effect that takes into account finite interface transparency, and explain this effect as arising due to different levels of disorder in the Pd layer. We believe the same proximity induced effect could also appear in other studies and will also affect ferromagnet/superconductor/ferromagnet structures.
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Jul 2007
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Abstract: [1] Paleoproterozioc (ca. 1.9 Ga) stromatolites from the Biwabik Iron-Formation (Minnesota, United States) contain fossil forms which in the literature have been attributed to ancient microbes including iron-oxidising bacteria and cyanobacteria. To search for valence state fossils, we measured Fe3+/?Fe (?Fe = Fe2+ + Fe3+) transverse to the laminae of a Biwabik, probably biogenic stromatolite and compared the results with a scan across the enclosing, likely abiotic sedimentary rock (or interstromatolite fill). To obtain Fe3+/?Fe and information about the site symmetry and crystal field strength, we used L3 (2p3/2 ? 3d) soft X-ray absorption spectroscopy and interpreted the measurements using our calculated spectra. We found that Fe3+/?Fe is approximately constant at 0.3 within the stromatolite, increases steeply to around 0.6 in the region of the stromatolite-fill boundary, and then reduces significantly in the interstromatolite fill. The crystal field strength for octahedral Fe3+ increased and became more irregular as the scan moved from the stromatolite into the fill. Our results tentatively suggest that a combination of ancient biological and later diagenetic processes can produce steep gradients in Fe3+/?Fe and alterations in the crystal field strength across a probable abiotic-biotic boundary. To describe the L3 absorption spectra in the stromatolite-fill region, it was necessary to include a significant Fe3+ tetrahedral component, which suggests the presence of magnetite. At other positions, fits using only octahedral Fe2+ and Fe3+ theoretical curves satisfactorily reproduce the spectra. The search for a possible new type of spatial biosignature in the valence state record for ancient stromatolites might help differentiate between the biogenic stromatolites and abiogenic stromatolite-like structures and could even be relevant to the search for fossil evidence of life in extraterrestrial rocks.
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Jul 2007
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Abstract: The structural parameters of ?-FeGe have been determined at ambient conditions using single crystal refinement. Powder diffraction has been carried out to determine structural properties and compressibility for pressures up to 30 GPa and temperatures as low as 82 K. The discontinuous change in the pressure dependence of the shortest Fe–Ge interatomic distance might be interpreted as a symmetry-conserving transition and seems to be related to a magnetic phase boundary line.
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Jul 2007
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I18-Microfocus Spectroscopy
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Jul 2007
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Moniek
Tromp
,
Sergio
Russu
,
Andy J.
Dent
,
J. Fred W.
Mosselmans
,
Ian
Harvey
,
Shu
Hayama
,
Andrea E.
Russell
,
Sam
Guerin
,
Brian E.
Hayden
,
Jens-peter
Suchsland
,
Ken
Meacham
,
Michael
Surridge
,
Jeremy G.
Frey
,
Nikolaos
Tsapatsaris
,
Angela M.
Beesley
,
Sven L. M.
Schroeder
,
Mark A.
Newton
,
Steven
Fiddy
,
Olga V.
Safonova
,
Pieter
Glatzel
,
Norman
Binsted
,
John
Evans
Abstract: High throughput screening methodologies are expanded to synchrotron based x‐ray absorption techniques. An environmental chamber, based on ultra‐high vacuum equipment, has been developed allowing in situ studies on arrays of samples while X‐ray absorption fine structure spectroscopy, Raman spectroscopy, mass spectrometry and/or X‐ray diffraction can be applied simultaneously to characterize the system under process conditions in a time‐resolved manner. The chamber accommodates a diverse range of samples from surface science to materials chemistry to heterogeneous catalysis. Data acquisition and data logging software is developed to handle large quantities of divers but related information. New data logging, processing and analysis procedures and programs are developed which will allow fast structure‐function relationships characterization.
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Jul 2007
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Abstract: Different mechanisms of formation of purely resonant reflections hhl (h = 2n + 1) during resonant diffraction of X-ray synchrotron radiation in zinc oxide, whose intensity very strongly changes with an increase in temperature, are considered. Such reflections, forbidden in the dipole-dipole scattering, can be excited owing to the dipole-quadrupole scattering and the anisotropy of X-ray susceptibility induced by thermal motion of atoms and point defects. Different contributions are theoretically considered and it is shown that they can be separated owing to their different temperature dependences.
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Jul 2007
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Abstract: The catalyzed reaction between NO and CO for NOx removal
is a key component of the role of rhodium in automotive
exhaust catalysts.[1] Kinetic models for this reaction have been
reported[2] with structural inferences based on Rh(111).
Surface-science studies have provided elegant descriptions
of surface oxidation (by O2).[3] However, the mean nuclearity
of the metal on Rh/Al2O3 during the reduction of NO by H2
varies with gas partial pressures and temperature.[4] Hence, an
assumption of an invariant core catalyst may be invalid for
highly dispersed catalysts. Indeed, combinations of CO and
NO at low temperatures (< 473 K) aggressively corrode
nanoparticulate rhodium to release Rh(CO)2 centers,[5]
which are mononuclear[6] and whose generation has also
been monitored kinetically.[7]
Our previous experiments showed that 5 wt% Rh/Al2O3,
prepared from rhodium trichloride, underwent structural
changes during a thermal ramp under a 1:1 mixture of 5%
CO/He and 5% NO/He.[5] At room temperature, the predominant
IR bands for the adsorbates were owing to
RhI
(CO)2 units and the mean Rh–Rh coordination number
was found to be approximately 3. By 473 K, the intensity of
the n(CO)as IR band (as = asymmetric) owing to Rh(CO)2
centers was just past its maximum.
In this study, the simultaneous monitoring of catalysts by
diffuse reflectance and time dependence of any structural
changes was monitored at 473 Kon a prereduced sample, with
the sequence starting under CO/He.
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Jul 2007
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Abstract: By using absorption and fluorescence spectroscopy, we compared the effects of heat and light treatments on the phycobilisome (PBS) antenna of Synechocystis sp. PCC 6803 cells. Fluorescence emission spectra obtained upon exciting predominantly PBS, recorded at 25 °C and 77 K, revealed characteristic changes upon heat treatment of the cells. A 5-min incubation at 50 °C, which completely inactivated the activity of photosystem II, led to a small but statistically significant decrease in the F680/F655 fluorescence intensity ratio. In contrast, heat treatment at 60 °C resulted in a much larger decrease in the same ratio and was accompanied by a blue-shift of the main PBS emission band at around 655 nm (F655), indicating an energetic decoupling of PBS from chlorophylls and reorganizations in its internal structure. (Upon exciting PBS, F680 originates from photosystem II and from the terminal emitter of PBS.). Very similar changes were obtained upon exposing the cells to high light (600–7500 μmol photons m−2 s−1) for different time periods (10 min to 3 h). In cells with heat-inactivated photosystem II, the variations caused by light treatment could clearly be assigned to a similar energetic decoupling of the PBS from the membrane and internal reorganizations as induced at around 60 °C. These data can be explained within the frameworks of thermo-optic mechanism [Cseh et al. 2000, Biochemistry 39, 15250]: in high light the heat packages originating from dissipation might lead to elementary structural changes in the close vicinity of dissipation in heat-sensitive structural elements, e.g. around the site where PBS is anchored to the membrane. This, in turn, brings about a diminishment in the energy supply from PBS to the photosystems and reorganization in the molecular architecture of PBS.
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Jun 2007
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Abstract: Change and change again: Under catalytic conditions for NO/CO conversion, simultaneous time-resolved extended X-ray absorption fine structure spectroscopy and IR studies show that the rhodium atoms in 5?wt?% Rh/Al2O3 rapidly migrate between CO-covered Rh particles and mononuclear Rh–NO sites depending on the changing gas composition. At lower temperatures (473?K), there is interconversion between mononuclear Rh(CO)2 and Rh(NO) centers.
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Jun 2007
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