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This contribution discusses the phenomena of retrograde condensation of one or two liquids. It w1 be shown that both phenomena can be well understood. Also the relation of retrograde condensation of one liquid phase with the condensation behavior of natural gas will be discussed. Similarly that of two liquid phases with multiple phase behavior occurring in low temperature reservoir fluids will be pointed out. 相似文献
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Kevin S. Peters 《Angewandte Chemie (International ed. in English)》1994,33(3):294-302
Why have molecules only been seen but not heard? For over a century chemists have probed reactions with various spectroscopic methods to learn about structures, dynamics, and reactivities of their molecules. What they have not done is to listen to their molecules react. Although the photoacoustic phenomenon has been known since 1880, it is only in the last twenty years that technology has developed to the point where sound waves produced by reacting molecules can be time resolved and the information contained within the waves deciphered. The information content within the photoacoustic wave is indeed rich, for one can learn about the dynamics and the magnitude of enthalpy changes associated with the reaction as well as the changes in molecular volume. This review article chronicles the development of time-resolved photoacoustic calorimetry and its application to a variety of reactions encountered in organic and organometallic chemistry and biochemistry. 相似文献
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Hans Peters Hans van der Stel Ton Storcken 《Mathematical Methods of Operations Research》1993,38(2):213-229
A voting scheme assigns to each profile of alternatives reported byn individuals a compromise alternative. A voting scheme is strategy-proof if no individual is better off by lying, i.e., not reporting a best alternative. In this paper the main results concern the case where the set of alternatives is the Euclidean plane and the preferences are Euclidean. It is shown that for strategy-proof voting schemes continuity is equivalent to convexity of the range of the voting scheme. Using a result by Kim and Roush (1984), this leads to characterizations of surjective or unanimous, anonymous, strategy-proof voting schemes.Furthermore, the paper contains an extensive discussion of related results in the area. 相似文献
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As ab initio electronic structure calculations become more accurate, inherent sources of error in classical transition state theory such as barrier recrossing and tunneling may become major sources of error in calculating rate constants. This paper introduces a general method for diabatically constructing the transverse eigensystem of a reaction path Hamiltonian in systems with many degenerate transverse frequencies. The diabatically constructed reaction path Hamiltonian yields smoothly varying coupling constants that, in turn, facilitate reactive flux calculations. As an example we compute the dynamically corrected rate constant for the chair to boat interconversion of cyclohexane, a system with 48 degrees of freedom and a number of degenerate frequencies. The transmission coefficients obtained from the reactive flux simulations agree with previous results that have been calculated using an empirical potential. Furthermore, the calculated rate constants agree with experimental values. Comparison to variational transition state theory shows that, despite finding the true bottleneck along the reaction pathway, variational transition state theory only accounts for half of the rate constant reduction due to recrossing trajectories. 相似文献