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Register a new userNonequilibrium Stationary Process and Fluctuation-Dissipation Relations
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A stochastic dynamics has a natural decomposition into a drift capturing mean rate of change and a martingale increment capturing randomness. They are two statistically uncorrelated, but not necessarily independent mechanisms contributing to the overall fluctuations of the dynamics, representing the uncertainties in the past and in the future. A generalized Einstein relation is a consequence solely because the dynamics being stationary; and the Green-Kubo formula reflects a balance between the two mechanisms. Equilibrium with reversibility is characterized by a novel covariance symmetry.
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We use a relationship between response and correlation function in nonequilibrium systems to establish a connection between the heat production and the deviations from the equilibrium fluctuation-dissipation theorem. This scheme extends the Harada-Sasa formulation [Phys. Rev. Lett. 95, 130602 (2005)], obtained for Langevin equations in steady states, as it also holds for transient regimes and for discrete jump processes involving small entropic changes. Moreover, a general formulation includes two times and the new concepts of two-time work, kinetic energy, and of a two-time heat exchange that can be related to a nonequilibrium effective temperature. Numerical simulations of a chain of anharmonic oscillators and of a model for a molecular motor driven by ATP hydrolysis illustrate these points.
Stochastic entropy production, which quantifies the difference between the probabilities of trajectories of a stochastic dynamics and its time reversals, has a central role in nonequilibrium thermodynamics. In the theory of probability, the change in the statistical properties of observables can be represented by a change in the probability measure. We consider operators on the space of probability measure that induce changes in the statistical properties of a process, and formulate entropy productions in terms of these change-of-probability-measure (CPM) operators. This mathematical underpinning of the origin of entropy productions allows us to achieve an organization of various forms of fluctuation relations: All entropy productions have a non-negative mean value, admit the integral fluctuation theorem, and satisfy a rather general fluctuation relation. Other results such as the transient fluctuation theorem and detailed fluctuation theorems then are derived from the general fluctuation relation with more constraints on the operator. We use a discrete-time, discrete-state-space Markov process to draw the contradistinction among three reversals of a process: time reversal, protocol reversal and the dual process. The properties of their corresponding CPM operators are examined, and the domains of validity of various fluctuation relations for entropy productions in physics and chemistry are revealed. We also show that our CPM operator formalism can help us rather easily extend other fluctuations relations for excess work and heat, discuss the martingale properties of entropy productions, and derive the stochastic integral formulas for entropy productions in constant-noise diffusion process with Girsanov theorem. Our formalism provides a general and concise way to study the properties of entropy-related quantities in stochastic thermodynamics and information theory.
We describe a simple method of umbrella trajectory sampling for Markov chains. The method allows the estimation of large-deviation rate functions, for path-extensive dynamic observables, for an arbitrary number of models within a certain family. The general relationship between probability distributions of dynamic observables of members of this family is an extended fluctuation relation. When the dynamic observable is chosen to be entropy production, members of this family include the forward Markov chain and its time reverse, whose probability distributions are related by the expected simple fluctuation relation.
By analogy with linear-response we formulate the duality and reciprocity properties of current and voltage fluctuations expressed by Nyquist relations including the intrinsic bandwidths of the respective fluctuations. For this purpose we individuate total-number and drift-velocity fluctuations of carriers inside a conductor as the microscopic sources of noise. The spectral densities at low frequency of the current and voltage fluctuations and the respective conductance and resistance are related in a mutual exclusive way to the corresponding noise-source. The macroscopic variance of current and voltage fluctuations are found to display a dual property via a plasma conductance that admits a reciprocal plasma resistance. Analogously, the microscopic noise-sources are found to obey a dual property and a reciprocity relation. The formulation is carried out in the frame of the grand canonical (for current noise) and canonical (for voltage noise) ensembles and results are derived which are valid for classical as well as for degenerate statistics including fractional exclusion statistics. The unifying theory so developed sheds new light on the microscopic interpretation of dissipation and fluctuation phenomena in conductors. In particular it is proven that, as a consequence of the Pauli principle, for Fermions non-vanishing single-carrier velocity fluctuations at zero temperature are responsible for diffusion but not for current noise, which vanishes in this limit.
Fluctuation-dissipation relations or theorems (FDTs) are fundamental for statistical physics and can be rigorously derived for equilibrium systems. Their applicability to non-equilibrium systems is, however, debated. Here, we simulate an active microrheology experiment, in which a spherical colloid is pulled with a constant external force through a fluid, creating near-equilibrium and far-from-equilibrium systems. We characterize the structural and dynamical properties of these systems, and reconstruct an effective generalized Langevin equation (GLE) for the colloid dynamics. Specifically, we test the validity of two FDTs: The first FDT relates the non-equilibrium response of a system to equilibrium correlation functions, and the second FDT relates the memory friction kernel in the GLE to the stochastic force. We find that the validity of the first FDT depends strongly on the strength of the external driving: it is fulfilled close to equilibrium and breaks down far from it. In contrast, we observe that the second FDT is always fulfilled. We provide a mathematical argument why this generally holds for memory kernels reconstructed from a deterministic Volterra equation for correlation functions, even for non-stationary non-equilibrium systems. Motivated by the Mori-Zwanzig formalism, we therefore suggest to impose an orthogonality constraint on the stochastic force, which is in fact equivalent to the validity of this Volterra equation. Such GLEs automatically satisfy the second FDT and are unique, which is desirable when using GLEs for coarse-grained modeling.
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