Shear-thickening and entropy-driven reentrance

We discuss a generic mechanism for shear thickening analogous to entropy-driven phase reentrance. We implement it in the context of nonrelaxational mean-field glassy systems: although very simple, the microscopic models we study present a dynamical phase diagram with second- and first-order stirring-induced jamming transitions leading to intermittency, metastability, and phase coexistence as seen in some experiments. The jammed state is fragile with respect to change in the stirring direction. Our approach provides a direct derivation of a mode-coupling theory of shear thickening.     

Edwards' measures for powders and glasses

Can one construct a thermodynamics for compact, slowly moving powders and grains? A few years ago, Edwards proposed a possible step in this direction, raising the fascinating perspective that such systems have a statistical mechanics of their own, different from that of Maxwell, Boltzmann, and Gibbs, allowing us to have some information while still ignoring dynamic details. Recent developments in the theory of glasses have come to confirm these ideas within mean field. In order to go beyond, we explicitly generate Edwards' measure in a 3D model. Comparison of the results with the irreversible compaction data shows very good agreement. The present framework immediately suggests new experimental checks.     

Amino acid-based dithiazines: synthesis and photofragmentation of their benzaldehyde adducts

Alpha-amino acids and GABA are functionalized with dithiazine rings via reaction with sodium hydrosulfide in aqueous formaldehyde. The resulting dithiazines are lithiated at -78 degrees C and reacted with benzaldehyde furnishing amino acid-based 2,5-bis-substituted dithiazines. These adducts undergo externally sensitized photofragmentation with quantum efficiency comparable to that of the parent dithiane adducts, thus offering a novel approach to amino acid-based photolabile tethers. [reaction: see text]     

Simulating structural transitions by direct transition current sampling: the example of LJ38

Reaction paths and probabilities are inferred, in a usual Monte Carlo or molecular dynamic simulation, directly from the evolution of the positions of the particles. The process becomes time-consuming in many interesting cases in which the transition probabilities are small. A radically different approach consists of setting up a computation scheme where the object whose time evolution is simulated is the transition current itself. The relevant timescale for such a computation is the one needed for the transition probability rate to reach a stationary level, and this is usually substantially shorter than the passage time of an individual system. As an example, we show, in the context of the "benchmark" case of 38 particles interacting via the Lennard-Jones potential ("LJ(38)" cluster), how this method may be used to explore the reactions that take place between different phases, recovering efficiently known results, and uncovering new ones with small computational effort.     

Canonically invariant formulation of Langevin and Fokker-Planck equations

We present a canonically invariant form for the generalized Langevin and Fokker-Planck equations. We discuss the role of constants of motion and the construction of conservative stochastic processes. Received : 24 July 1997 / Revised : 30 October 1997 / Accepted : 26 January 1998     

Direct evaluation of large-deviation functions

We introduce a numerical procedure to evaluate directly the probabilities of large deviations of physical quantities, such as current or density, that are local in time. The large-deviation functions are given in terms of the typical properties of a modified dynamics, and since they no longer involve rare events, can be evaluated efficiently and over a wider ranges of values. We illustrate the method with the current fluctuations of the Totally Asymmetric Exclusion Process and with the work distribution of a driven Lorentz gas.     

Simulating Rare Events in Dynamical Processes

Atypical, rare trajectories of dynamical systems are important: they are often the paths for chemical reactions, the haven of (relative) stability of planetary systems, the rogue waves that are detected in oil platforms, the structures that are responsible for intermittency in a turbulent liquid, the active regions that allow a supercooled liquid to flow…. Simulating them in an efficient, accelerated way, is in fact quite simple.     

Photoinduced signal amplification through controlled externally sensitized fragmentation in masked sensitizers

Addition of lithiated dithianes to diaryl ketones, potential electron-transfer sensitizers, disrupts conjugation between the two aromatic moieties, effectively masking the sensitizer. A novel photoamplification strategy is developed based on photosensitized cleavage in such adducts, where each fragmentation event releases more diaryl ketone, capable of sensitization. As a result, mass release of dithianes, triggered with a very small amount of the initiator, is observed. Such amplified release can be made contingent on a molecular recognition event, offering a promising methodology for high throughput bioanalytical applications. The concept is proved with the use of micro- and nanosized polymeric supports, including dendrimers.