There are only a very few known relations in statistical dynamics that are valid for systems driven arbitrarily far-from-equilibrium. One of these is the fluctuation theorem, which places conditions on the entropy production probability distribution of nonequilibrium systems. Another recently discovered far from equilibrium expression relates nonequilibrium measurements of the work done on a sy...

A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a nonequilibrium ensemble is that it is larger than that of the same system at equilibrium. Herein, we derive a formally exact expression for the probability distribution o...

The one to one correspondence between the existence of a unique equilibrium state and the differentiability of the free energy density with respect to the external field previously shown for Ising ferromagnets is extendend to higher valued spin systems as well as to continuum systems satisfying the Fortuin, Kasteleyn and Ginibre inequalities. In particular this is shown to hold for a mixture of...

The observed equilibrium constants (Kobs) of the malate dehydrogenase (EC 1.1.1.37), citrate synthase (EC 4.1.3.7) and citrate lyase (EC 4.1.3.6) reactions have been determined under near physiological conditions (38”, pH 7.0, Z = 0.25, free [Mg”+] = 10u3 M). From these values the observed standard free energy change (AGibs) for the hydrolysis of acetyl-CoA has been determined. Under the above ...

an extended peng-robinson equation of state (epr-eos) is used to model the vapor-liquid equilibrium (vle) in systems containing (water + nacl + co2), (water + methanol + nacl + co2), (water + na2so4 + co2) and (water + nh4cl + co2). the binary and ternary interaction parameters between salt and solvent are adjusted to experimental mean solvent activity of salts (nacl and na2so4). for the system...

We present an approach to the estimate of the potential of mean force along a generic reaction coordinate based on maximum likelihood methods and path-ensemble averages in systems driven far from equilibrium. Following similar arguments, various free energy estimators can be recovered, all providing comparable computational accuracy. The method, applied to the unfolding process of the alpha -he...

Using the replica trick we derive a formalism to describe the structure and the thermodynamic properties of a binary liquid in equilibrium with a porous medium. We present the replica Ornstein-Zernike equations for the general case of a k-component liquid inside a porous matrix; besides the usual liquid-state closure relations, we consider in particular the optimized random phase approximation ...

Periodic microphases universally emerge in systems for which short-range interparticle attraction is frustrated by long-range repulsion. The morphological richness of these phases makes them desirable material targets, but our relatively coarse understanding of even simple models hinders controlling their assembly. We report here the solution of the equilibrium phase behavior of a microscopic m...

The contribution to the free energy for a film of liquid of thickness h on a solid surface due to the interactions between the solid-liquid and liquid-gas interfaces is given by the binding potential, g(h). The precise form of g(h) determines whether or not the liquid wets the surface. Note that differentiating g(h) gives the Derjaguin or disjoining pressure. We develop a microscopic density fu...

Abstract This paper establishes relationships between static Nash equilibria and dynamic Markov perfect equilibria of tariff and quota retaliation games. In supermodular games where tariffs are strategic complements, the steady state of every, symmetric Markov perfect equilibrium must have lower tariffs than in the static equilibrium. If tariffs are strategic substitutes, tariffs in the dynamic...