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Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry. 相似文献
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Elola MD Ladanyi BM Scodinu A Loughnane BJ Fourkas JT 《The journal of physical chemistry. B》2005,109(50):24085-24099
In this work we have studied the relaxation dynamics of the many-body polarizability anisotropy in liquid mixtures of benzene (Bz) and hexafluorobenzene (Hf) at room temperature by femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES) experiments and molecular dynamics (MD) simulations. The computed polarizability response arising from intermolecular interactions was included using the first-order dipole-induced-dipole model with the molecular polarizability distributed over the carbon sites of each molecule. We found good qualitative agreement between experiments and simulations in the features exhibited by the nuclear response function R(t) for pure liquids and mixtures. The long-time diffusive decay of R(t) was observed to vary substantially with composition, slowing down noticeably with dilution of each of the species as compared with that in the corresponding pure liquids. MD simulation shows that the effect on R(t) is due to the formation of strong and localized intermolecular association between Bz and Hf species that hinder the rotational diffusive dynamics. The formation of these Bz-Hf complexes in the liquid mixtures also modifies the rotational diffusive dynamics of the component species in such a way that cannot be explained solely in terms of a viscosity effect. Even though the computed orientational diffusive relaxation times associated with Bz and Hf are larger by a factor of approximately 2 than those from experiments, we found similar trends in experiments and simulations for these characteristic times as a function of composition. Namely, the collective and single-molecule orientational correlation times associated with Bz are observed to grow monotonically with the dilution of Bz, while those corresponding to Hf species exhibit a maximum at the equimolar composition. We attribute the quantitative discrepancy between experiments and simulations to the use of the Williams potential, which seems to overestimate the intermolecular interactions and thus predicts not only a slower translational dynamics but also a slower rotational diffusion dynamics than in real fluids. 相似文献
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