Novel nitrogen-based organosulfur electrodes for advanced intermediate temperature batteries

Advanced secondary batteries operating at intermediate temperatures (100 to 200 C) have attracted considerable interest due to their inherent advantages (reduced corrosion and safety risks) over higher temperature systems. Current work in this laboratory has involved research on a class of intermediate temperature Na/beta double prime- alumina/RSSR batteries conceptually similar to Na/S cells, but operating within a temperature range of 100 to 150 C, and having an organosulfur rather than inorganic sulfur positive electrode. The organosulfur electrodes are based on the reversible, two electron eduction of organodisulfides to the corresponding thiolate anions, RSSR + 2 electrons yield 2RS(-), where R is an organic moiety. Among the advantages of such a generic redox couple for battery research is the ability to tailor the physical, chemical, and electrochemical properties of the RSSR molecule through choice of the organic moiety. The viscosity, liquidus range, dielectric constant, equivalent weight, and redox potential can in fact be verified in a largely predictable manner. The current work concerns the use of multiple nitrogen organosulfur molecules, chosen for application in Na/RSSR cells for their expected oxidizing character. In fact, a Na/RSSR cell containing one of these materials, the sodium salt of 5-mercapto 1-methyltetrazole, yielded the highest open circuit voltage obtained yet in the laboratory; 3.0 volts in the charged state and 2.6 volts at 100 percent discharge. Accordingly, the cycling behavior of a series of multiple nitrogen organodisulfides as well as polymeric organodisulfides are presented in this manuscript

Spatial fluctuations at vertices of epithelial layers: quantification of regulation by Rho pathway

In living matter, shape fluctuations induced by acto-myosin are usually studied in vitro via reconstituted gels, whose properties are controlled by changing the concentrations of actin, myosin and cross-linkers. Such an approach deliberately avoids to consider the complexity of biochemical signaling inherent to living systems. Acto-myosin activity inside living cells is mainly regulated by the Rho signaling pathway which is composed of multiple layers of coupled activators and inhibitors. We investigate how such a pathway controls the dynamics of confluent epithelial tissues by tracking the displacements of the junction points between cells. Using a phenomenological model to analyze the vertex fluctuations, we rationalize the effects of different Rho signaling targets on the emergent tissue activity by quantifying the effective diffusion coefficient, the persistence time and persistence length of the fluctuations. Our results reveal an unanticipated correlation between layers of activation/inhibition and spatial fluctuations within tissues. Overall, this work connects the regulation via biochemical signaling with mesoscopic spatial fluctuations, with potential application to the study of structural rearrangements in epithelial tissues.Comment: 8 pages, 3 figure

Relevance of initial and final conditions for the Fluctuation Relation in Markov processes

Numerical observations on a Markov chain and on the continuous Markov process performed by a granular tracer show that the ``usual'' fluctuation relation for a given observable is not verified for finite (but arbitrarily large) times. This suggests that some terms which are usually expected to be negligible, i.e. ``border terms'' dependent only on initial and final states, in fact cannot be neglected. Furthermore, the Markov chain and the granular tracer behave in a quite similar fashion.Comment: 23 pages, 5 figures, submitted to JSTA

Injected Power Fluctuations in 1D Dissipative Systems

Using fermionic techniques, we compute exactly the large deviation function (ldf) of the time-integrated injected power in several one-dimensional dissipative systems of classical spins. The dynamics are T=0 Glauber dynamics supplemented by an injection mechanism, which is taken as a Poissonian flipping of one particular spin. We discuss the physical content of the results, specifically the influence of the rate of the Poisson process on the properties of the ldf.Comment: 18 pages, 8 figure

Entropy production and fluctuation theorems under feedback control: the molecular refrigerator model revisited

We revisit the model of a Brownian particle in a heat bath submitted to an actively controlled force proportional to the velocity that leads to thermal noise reduction (cold damping). We investigate the influence of the continuous feedback on the fluctuations of the total entropy production and show that the explicit expression of the detailed fluctuation theorem involves different dynamics and observables in the forward and backward processes. As an illustration, we study the analytically solvable case of a harmonic oscillator and calculate the characteristic function of the entropy production in a nonequilibrium steady state. We then determine the corresponding large deviation function which results from an unusual interplay between 'boundary' and 'bulk' contributions.Comment: 16 pages, 5 figures. References 9,10,13,14,15 added. A few changes in the text. Accepted for publication in J. Stat. Mec

Is it possible to experimentally verify the fluctuation relation? A review of theoretical motivations and numerical evidence

The theoretical motivations to perform experimental tests of the stationary state fluctuation relation are reviewed. The difficulties involved in such tests, evidenced by numerical simulations, are also discussed.Comment: 36 pages, 4 figures. Extended version of a presentation to the discussion "Is it possible to experimentally verify the fluctuation theorem?", IHP, Paris, December 1, 2006. Comments are very welcom

Fluctuations in granular gases

A driven granular material, e.g. a vibrated box full of sand, is a stationary system which may be very far from equilibrium. The standard equilibrium statistical mechanics is therefore inadequate to describe fluctuations in such a system. Here we present numerical and analytical results concerning energy and injected power fluctuations. In the first part we explain how the study of the probability density function (pdf) of the fluctuations of total energy is related to the characterization of velocity correlations. Two different regimes are addressed: the gas driven at the boundaries and the homogeneously driven gas. In a granular gas, due to non-Gaussianity of the velocity pdf or lack of homogeneity in hydrodynamics profiles, even in the absence of velocity correlations, the fluctuations of total energy are non-trivial and may lead to erroneous conclusions about the role of correlations. In the second part of the chapter we take into consideration the fluctuations of injected power in driven granular gas models. Recently, real and numerical experiments have been interpreted as evidence that the fluctuations of power injection seem to satisfy the Gallavotti-Cohen Fluctuation Relation. We will discuss an alternative interpretation of such results which invalidates the Gallavotti-Cohen symmetry. Moreover, starting from the Liouville equation and using techniques from large deviation theory, the general validity of a Fluctuation Relation for power injection in driven granular gases is questioned. Finally a functional is defined using the Lebowitz-Spohn approach for Markov processes applied to the linear inelastic Boltzmann equation relevant to describe the motion of a tracer particle. Such a functional results to be different from injected power and to satisfy a Fluctuation Relation.Comment: 40 pages, 18 figure

Lower bounds on dissipation upon coarse graining

By different coarse-graining procedures we derive lower bounds on the total mean work dissipated in Brownian systems driven out of equilibrium. With several analytically solvable examples we illustrate how, when, and where the information on the dissipation is captured.Comment: 11 pages, 8 figure

Heat flow in chains driven by thermal noise

We consider the large deviation function for a classical harmonic chain composed of N particles driven at the end points by heat reservoirs, first derived in the quantum regime by Saito and Dhar and in the classical regime by Saito and Dhar and Kundu et al. Within a Langevin description we perform this calculation on the basis of a standard path integral calculation in Fourier space. The cumulant generating function yielding the large deviation function is given in terms of a transmission Green's function and is consistent with the fluctuation theorem. We find a simple expression for the tails of the heat distribution which turn out to decay exponentially. We, moreover, consider an extension of a single particle model suggested by Derrida and Brunet and discuss the two-particle case. We also discuss the limit for large N and present a closed expression for the cumulant generating function. Finally, we present a derivation of the fluctuation theorem on the basis of a Fokker-Planck description. This result is not restricted to the harmonic case but is valid for a general interaction potential between the particles.Comment: Latex: 26 pages and 9 figures, appeared in J. Stat. Mech. P04005 (2012

Enhanced Pulse Propagation in Non-Linear Arrays of Oscillators

The propagation of a pulse in a nonlinear array of oscillators is influenced by the nature of the array and by its coupling to a thermal environment. For example, in some arrays a pulse can be speeded up while in others a pulse can be slowed down by raising the temperature. We begin by showing that an energy pulse (1D) or energy front (2D) travels more rapidly and remains more localized over greater distances in an isolated array (microcanonical) of hard springs than in a harmonic array or in a soft-springed array. Increasing the pulse amplitude causes it to speed up in a hard chain, leaves the pulse speed unchanged in a harmonic system, and slows down the pulse in a soft chain. Connection of each site to a thermal environment (canonical) affects these results very differently in each type of array. In a hard chain the dissipative forces slow down the pulse while raising the temperature speeds it up. In a soft chain the opposite occurs: the dissipative forces actually speed up the pulse while raising the temperature slows it down. In a harmonic chain neither dissipation nor temperature changes affect the pulse speed. These and other results are explained on the basis of the frequency vs energy relations in the various arrays