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In the context of driven diffusive systems, for thermodynamic transformations over a large but finite time window, we derive an expansion of the energy balance. In particular, we characterize the transformations which minimize the energy dissipation and describe the optimal correction to the quasi-static limit. Surprisingly, in the case of transformations between homogeneous equilibrium states of an ideal gas, the optimal transformation is a sequence of inhomogeneous equilibrium states.
We consider a continuous time Markov chain on a countable state space. We prove a joint large deviation principle (LDP) of the empirical measure and current in the limit of large time interval. The proof is based on results on the joint large deviati ons of the empirical measure and flow obtained in cite{BFG}. By improving such results we also show, under additional assumptions, that the LDP holds with the strong L^1 topology on the space of currents. We deduce a general version of the Gallavotti-Cohen (GC) symmetry for the current field and show that it implies the so-called fluctuation theorem for the GC functional. We also analyze the large deviation properties of generalized empirical currents associated to a fundamental basis in the cycle space, which, as we show, are given by the first class homological coefficients in the graph underlying the Markov chain. Finally, we discuss in detail some examples.
We consider the Cahn-Hilliard equation in one space dimension, perturbed by the derivative of a space and time white noise of intensity $epsilon^{frac 12}$, and we investigate the effect of the noise, as $epsilon to 0$, on the solutions when the init ial condition is a front that separates the two stable phases. We prove that, given $gamma< frac 23$, with probability going to one as $epsilon to 0$, the solution remains close to a front for times of the order of $epsilon^{-gamma}$, and we study the fluctuations of the front in this time scaling. They are given by a one dimensional continuous process, self similar of order $frac 14$ and non Markovian, related to a fractional Brownian motion and for which a couple of representations are given.
We recover the Donsker-Varadhan large deviations principle (LDP) for the empirical measure of a continuous time Markov chain on a countable (finite or infinite) state space from the joint LDP for the empirical measure and the empirical flow proved in [2].
We consider a macroscopic system in contact with boundary reservoirs and/or under the action of an external field. We discuss the case in which the external forcing depends explicitly on time and drives the system from a nonequilibrium state to anoth er one. In this case the amount of energy dissipated along the transformation becomes infinite when an unbounded time window is considered. Following the general proposal by Oono and Paniconi and using results of the macroscopic fluctuation theory, we give a natural definition of a renormalized work. We then discuss its thermodynamic relevance by showing that it satisfies a Clausius inequality and that quasi static transformations minimize the renormalized work. In addition, we connect the renormalized work to the quasi potential describing the fluctuations in the stationary nonequilibrium ensemble. The latter result provides a characterization of the quasi potential that does not involve rare fluctuations.
In this paper we present a self-contained macroscopic description of diffusive systems interacting with boundary reservoirs and under the action of external fields. The approach is based on simple postulates which are suggested by a wide class of mic roscopic stochastic models where they are satisfied. The description however does not refer in any way to an underlying microscopic dynamics: the only input required are transport coefficients as functions of thermodynamic variables, which are experimentally accessible. The basic postulates are local equilibrium which allows a hydrodynamic description of the evolution, the Einstein relation among the transport coefficients, and a variational principle defining the out of equilibrium free energy. Associated to the variational principle there is a Hamilton-Jacobi equation satisfied by the free energy, very useful for concrete calculations. Correlations over a macroscopic scale are, in our scheme, a generic property of nonequilibrium states. Correlation functions of any order can be calculated from the free energy functional which is generically a non local functional of thermodynamic variables. Special attention is given to the notion of equilibrium state from the standpoint of nonequilibrium.
Experiments show that macroscopic systems in a stationary nonequilibrium state exhibit long range correlations of the local thermodynamic variables. In previous papers we proposed a Hamilton-Jacobi equation for the nonequilibrium free energy as a bas ic principle of nonequilibrium thermodynamics. We show here how an equation for the two point correlations can be derived from the Hamilton-Jacobi equation for arbitrary transport coefficients for dynamics with both external fields and boundary reservoirs. In contrast with fluctuating hydrodynamics, this approach can be used to derive equations for correlations of any order. Generically, the solutions of the equation for the correlation functions are non-trivial and show that long range correlations are indeed a common feature of nonequilibrium systems. Finally, we establish a criterion to determine whether the local thermodynamic variables are positively or negatively correlated in terms of properties of the transport coefficients.
This paper provides an introduction to some stochastic models of lattice gases out of equilibrium and a discussion of results of various kinds obtained in recent years. Although these models are different in their microscopic features, a unified pict ure is emerging at the macroscopic level, applicable, in our view, to real phenomena where diffusion is the dominating physical mechanism. We rely mainly on an approach developed by the authors based on the study of dynamical large fluctuations in stationary states of open systems. The outcome of this approach is a theory connecting the non equilibrium thermodynamics to the transport coefficients via a variational principle. This leads ultimately to a functional derivative equation of Hamilton-Jacobi type for the non equilibrium free energy in which local thermodynamic variables are the independent arguments. In the first part of the paper we give a detailed introduction to the microscopic dynamics considered, while the second part, devoted to the macroscopic properties, illustrates many consequences of the Hamilton-Jacobi equation. In both parts several novelties are included.
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