We consider thermodynamically consistent autonomous Markov jump processes displaying a macroscopic limit in which the logarithm of the probability distribution is proportional to a scale-independent rate function (i.e. a large deviations principle is satisfied). In order to provide an explicit expression for the probability distribution valid away from equilibrium, we propose a linear response theory performed at the level of the rate function. We show that the first order non-equilibrium contribution to the steady state rate function, g(x), satisfies u(x). del g(x) = -beta(W) over dot(x) u (x) defines the macroscopic deterministic dynamics, and the scalar field (W) over dot(x) x. This equation provides a practical way to determine g(x), significantly outperforms standard linear response theory applied at the level of the probability distribution, and approximates the rate function surprisingly well in some far-from-equilibrium conditions. The method applies to a wealth of physical and chemical systems, that we exemplify by two analytically tractable models-an electrical circuit and an autocatalytic chemical reaction network-both undergoing a non-equilibrium transition from a monostable phase to a bistable phase. Our approach can be easily generalized to transient probabilities and non-autonomous dynamics. Moreover, its recursive application generates a virtual flow in the probability space which allows to determine the steady state rate function arbitrarily far from equilibrium.
Linear response in large deviations theory: a method to compute non-equilibrium distributions
Falasco, Gianmaria;
2021
Abstract
We consider thermodynamically consistent autonomous Markov jump processes displaying a macroscopic limit in which the logarithm of the probability distribution is proportional to a scale-independent rate function (i.e. a large deviations principle is satisfied). In order to provide an explicit expression for the probability distribution valid away from equilibrium, we propose a linear response theory performed at the level of the rate function. We show that the first order non-equilibrium contribution to the steady state rate function, g(x), satisfies u(x). del g(x) = -beta(W) over dot(x) u (x) defines the macroscopic deterministic dynamics, and the scalar field (W) over dot(x) x. This equation provides a practical way to determine g(x), significantly outperforms standard linear response theory applied at the level of the probability distribution, and approximates the rate function surprisingly well in some far-from-equilibrium conditions. The method applies to a wealth of physical and chemical systems, that we exemplify by two analytically tractable models-an electrical circuit and an autocatalytic chemical reaction network-both undergoing a non-equilibrium transition from a monostable phase to a bistable phase. Our approach can be easily generalized to transient probabilities and non-autonomous dynamics. Moreover, its recursive application generates a virtual flow in the probability space which allows to determine the steady state rate function arbitrarily far from equilibrium.File | Dimensione | Formato | |
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