We derive an extension of the mode-coupling theory for the liquid-glass transition to a class of models of confined fluids, where the fluid particles evolve in a disordered array of interaction sites. We find that the corresponding equations are similar to those describing the bulk, implying that the methods of investigation which were developed there are directly transferable to this new domain of application. We then compute the dynamical phase diagram of a simple model system and show that new and nontrivial transition scenarios, including reentrant glass transitions and higher-order singularities, can be predicted from the proposed theory.
A combined use of DFT periodic calculations and spectroscopic studies (IR and solid-state NMR) shows that a gamma-alumina treated at 500 degrees C under high vacuum contains surface defects, which are very reactive toward H2 or CH4. The reaction of H2 on defect sites occurs at low temperature (ca. 25 degrees C) on two types of Al atoms of low coordination numbers, AlIII or AlIV, to give AlIV-H and AlV-H, respectively. The amount of defects as titrated by H2 at 25 and 150 degrees C is 0.043 and 0.069 site/nm2, respectively, in comparison with 4 OH/nm2). In contrast, CH4 reacts selectively at 100-150 degrees C on the most reactive AlIII sites to form the corresponding AlIV-CH3 (0.030 site/nm2). The difference of reactivity of H2 and CH4 is fully consistent with calculations (reaction and activation energy, DeltaE and DeltaE++).
We derive a mode-coupling theory for the slow dynamics of fluids confined in disordered porous media represented by spherical particles randomly placed in space. Its equations display the usual nonlinear structure met in this theoretical framework, except for a linear contribution to the memory kernel which adds to the usual quadratic term. The coupling coefficients involve structural quantities which are specific of fluids evolving in random environments and have expressions which are consistent with those found in related problems. Numerical solutions for two simple models with pure hard core interactions lead to the prediction of a variety of glass transition scenarios, which are either continuous or discontinuous and include the possibility of higher-order singularities and glass-glass transitions. The main features of the dynamics in the two most generic cases are reviewed and illustrated with detailed computations. Moreover, a reentry phenomenon is predicted in the low fluid-high matrix density regime and is interpreted as the signature of a de-correlation mechanism by fluid-fluid collisions competing with the localization effect of the solid matrix.
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