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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)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5) IrCl21-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)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5)IrCl21-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)RhCl21-P-PPh2Py)]3, [(η5-C5Me5)IrCl21-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   
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An optimal control model of exhaustible resources is used to clarify the long run relationship between mineral rent and depletion cost at the industry level. A standard first order condition of the time rate of change of rents is reformulated to reveal that rent data may be used to help forecast the rise in extraction costs resulting from resource depletion. This application of the theory of exhaustible resources is illustrated using historical mineral industry rent and extraction cost data. A forecast of U.S. coal extraction costs, following the method proposed in this paper, suggests that future rates of extraction cost increases will be similar to rates experienced in the past.  相似文献   
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We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.  相似文献   
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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   
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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   
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The excitation of eigen surface waves by tubular electron beams in cylindrical discharge devices is studied. The influence of the wave‐field azimuthal structure on the excitation efficiency and nonlinear stage of the plasmabeam instability is investigated both numerically and analytically. Analytical expressions for the saturation amplitude and excitation efficiency of the wave under study are derived. They are found to agree well with results obtained by numerical modelling of the plasma‐beam interaction presented in this paper. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
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