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1.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
2.
Open circuit voltage (OCV) measurements in H2O/air concentration cells at T<580 K using Yb-doped SrCeO3 electrolyte indicate that under these conditions, protons are transported through the electrolyte as -ve ions, possibly as
hydroxyl (OH−) ions. The H+ ionic transport, which is generally reported, becomes the dominant mode for H2O/air concentration cells at temperatures greater than 750 K or when H2O/air electrodes are replaced by H2/Ar, and the anomalous OCV sign disappears. The combination of low temperature and the presence of hydrogen and oxygen as
provided by the H2O/air system appears to be necessary for the postulated hydroxyl ion electrode reactions to take place.
In addition to OCV measurements, results from impedance spectroscopy are used to provide evidence in support of the suggested
hydroxyl ion mode of protonic transport under the specified conditions. These findings are directly relevant in the development
of novel humidity sensors in the temperature range 450–580K and is reported in a separate paper in this conference.
Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996 相似文献
3.
We consider the growth of a spherical crystal in a supersaturatedsolution. In the first part, existence and uniqueness resultsfor radially symmetric growth are obtained, provided that thesupersaturation is not too large; conversely, when the far-fieldsupersaturation exceeds a critical value, it is shown that theradially symmetric solution ceases to exist in finite time.In the second part, we examine the linear stability of a radiallysymmetric similarity solution (in which the radius grows ast?) to shape perturbations. The results are compared with previousquasi-static analyses, and, in particular, the critical radiusat which the crystal becomes unstable is found to be largerfor small supersaturations, but smaller for large supersaturations,than those predicted by the quasi-static analysis 相似文献
4.
5.
R. J. Hinde 《Few-Body Systems》2006,38(2-4):187-191
We compute the vibrational coupling between two H2 molecules from ab initio quantum chemical calculations of the H2-H2 potential carried out at the full configuration interaction level of theory using the atom-centered aug-cc-pVTZ basis set
for hydrogen. We compare the full configuration interaction results with those obtained using two variants of coupled cluster
theory and find that a fully iterative treatment of connected triples may be required to estimate the H2-H2 vibrational coupling accurately using coupled cluster theory. 相似文献
6.
7.
A simple scheme is developed for treatment of vertical bed topography in shallow water flows. The effect of the vertical step on flows is modelled with the shallow water equations including local energy loss terms. The bed elevation is denoted with zb‐ for the left and zb+ for the right values at each grid point, hence exactly representing a discontinuity in the bed topography. The surface gradient method (SGM) is generalized to reconstruct water depths at cell interfaces involving a vertical step so that the fluxes at the cell interfaces can accurately be calculated with a Riemann solver. The scheme is verified by predicting a surge crossing a step, a tidal flow over a step and dam‐break flows on wet/dry beds. The results have shown good agreements compared with analytical solutions and available experimental data. The scheme is efficient, robust, and may be used for practical flow calculations. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
8.
9.
In intonation research, prominence-lending pitch movements have either been described on a linear or on a logarithmic frequency scale. An experiment has been carried out to check whether pitch movements in speech intonation are perceived on one of these two scales or on a psychoacoustic scale representing the frequency selectivity of the auditory system. This last scale is intermediary between the other two scales. Subjects matched the excursion size of prominence-lending pitch movements in utterances resynthesized in different pitch registers. Their task was to adjust the excursion size in a comparison stimulus in such a way that it lent equal prominence to the corresponding syllable in a fixed test stimulus. The comparison stimulus and the test stimulus had pitches running parallel on either the logarithmic frequency scale, the psychoacoustic scale, or the linear frequency scale. In one-half of the experimental sessions, the test stimulus was presented in the low register, while the comparison stimulus was presented in the high register, and, conversely, for the other half of the sessions. The result is that, in all cases, stimuli are matched in such a way that the average excursion sizes in different registers are equal on the psychoacoustic scale. 相似文献
10.
The adsorption of hydrogen on a clean Cu10%/Ni90% (110) alloy single crystal was studied using flash desorption spectroscopy (FDS), Auger electron spectroscopy (AES), and work function measurements. Surface compositions were varied from 100% Ni to 35% Ni. The hydrogen chemisorption on a-surface of 100% nickel revealed strong attractive interactions between the hydrogen atoms in accordance with previous work on Ni(100). Three desorption states (β1, β2 and α) appeared in the desorption spectra. The highest temperature (α) state was occupied only after the initial population of the β2-state. As the amount of copper was increased in the nickel substrate, desorption from the higher energy binding α-state was reduced, indicating a decrease in the attractive interactions among hydrogen atoms. The hydrogen coverage at saturation was not affected by the addition of copper to the nickel substrate until the copper concentration was greater than 25% at which a sharp reduction in saturation coverage occurred. This phenomenon was apparently due to the adsorption of hydrogen on Ni atoms followed by occupation of NiNi and CuNi bridged adsorption sites, while occupation of CuCu sites was restricted due to an energy barrier to migration. 相似文献