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Second Shell (second + shell)
Selected AbstractsTl(I)-the strongest structure-breaking metal ion in water?JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2007A quantum mechanical/molecular mechanical simulation study Abstract Structural and dynamical properties of the Tl(I) ion in dilute aqueous solution have been investigated by ab initio quantum mechanics in combination with molecular mechanics. The first shell plus a part of the second shell were treated by quantum mechanics at Hartree-Fock level, the rest of the system was described by an ab initio constructed potential. The radial distribution functions indicate two different bond lengths (2.79 and 3.16 Å) in the first hydration shell, in good agreement with large-angle X-ray scattering and extended X-ray absorption fine structure spectroscopy results. The average first shell coordination number was found as 5.9, and several other structural parameters such as coordination number distributions, angular distribution functions, and tilt- and ,-angle distributions were evaluated. The ion,ligand vibration spectrum and reorientational times were obtained via velocity auto correlation functions. The TlO stretching force constant is very weak with 5.0 N m,1. During the simulation, numerous water exchange processes took place between first and second hydration shell and between second shell and bulk. The mean ligand residence times for the first and second shell were determined as 1.3 and 1.5 ps, respectively, indicating Tl(I) to be a typical "structure-breaker". The calculated hydration energy of ,84 ± 16 kcal mol,1 agrees well with the experimental value of ,81 kcal mol,1. All data obtained for structure and dynamics of hydrated Tl(I) characterize this ion as a very special case among all monovalent metal ions, being the most potent "structure-breaker", but at the same time forming a distinct second hydration shell and thus having a far-reaching influence on the solvent structure. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Three metamorphic events recorded in a single garnet: Integrated phase modelling, in situ LA-ICPMS and SIMS geochronology from the Moine Supergroup, NW ScotlandJOURNAL OF METAMORPHIC GEOLOGY, Issue 3 2010K. A. CUTTS Abstract In situ LA-ICP-MS monazite geochronology from a garnet-bearing diatexite within the Moine Supergroup (Glenfinnan Group) NW Scotland records three temporally distinct metamorphic events within a single garnet porphyroblast. The initial growth of garnet occurred in the interval c. 825,780 Ma, as recorded by monazite inclusions located in the garnet core. Modelled P,T conditions based on the preserved garnet core composition indicate an initially comparatively high geothermal gradient regime and peak conditions of ,650 °C and 7 kbar. Monazite within a compositionally distinct second shell of garnet has an age of 724 ± 6 Ma. This is indistinguishable from a SIMS age of 725 ± 4 Ma obtained from metamorphic zircon in the sample, which is interpreted to record the timing of migmatization. This second stage of garnet growth occurred on a P,T path from ,6 kbar and 650 °C rising to ,9 kbar and 700 °C, with the peak conditions associated with partial melting. A third garnet zone which forms the rim contains monazite with an age of 464 ± 3 Ma. Monazite in the surrounding matrix has an age of 462 ± 2 Ma. This corresponds well with a U,Pb SIMS zircon age of 463 ± 4 Ma obtained from a deformed pegmatite that was emplaced during widespread folding and reworking of the migmatite fabric. The P,T conditions associated with the final phase of garnet growth were ,7 kbar and 650 °C. The monazite ages coupled with the phase relations modelled from this multistage garnet indicate that it records two Neoproterozoic tectonothermal events as well as the widespread Ordovician Grampian event associated with Caledonian orogenesis. Thus, this single garnet records much of the Neoproterozoic to Ordovician thermal history in NW Scotland, and highlights the long history of porphyroblast growth that can be revealed by in situ isotopic dating and associated P,T modelling. This approach has the potential to reveal much of the thermal architecture of Neoproterozoic events within the Moine Supergroup, despite intense Caledonian reworking, if suitable textural and mineralogical relationships can be indentified elsewhere. [source] Determination of the local structure of the first and second shells in ordered and disordered Ni,Mn alloysJOURNAL OF SYNCHROTRON RADIATION, Issue 2 2001A. V. Ryazhkin The coordination numbers and the interatomic distances for 50, 75 and 80 at.% Ni-Mn alloys in ordered and disordered states are presented. A new method for determining the first and second nearest neighbor coordination numbers in a binary alloy is applied. It is shown that magnetic properties of these alloys depend on short range order in atomic arrangement. [source] Chemical Speciation of Trace Zinc in Ordinary Portland Cement Using X-ray Absorption Fine Structure AnalysisJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2004Isao Tsuyumoto Chemical change of trace zinc in ordinary portland cement (205.1 ppm) was investigated in hydration process using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Intensities of the peaks appearing at the same energy of ZnO in XANES spectra were decreased with cement hydration. The interatomic distances and the coordination numbers of the first and the second shells calculated from EXAFS spectra indicated that ZnO hydrolyzed to zincate ion [Zn(OH)4]2, with cement hydration keeping their fundamental structure of ZnO4 tetrahedra. [source] | ||||||||||