The nonequilibrium Time-Reversible Baker Map provides simple illustrations of the Fluctuation Theorem, the Central Limit Theorem, and the Biased Random Walk. This is material in preparation for the Book form of Carol's and my 2016 Kharagpur Lectures.
Deterministic and time-reversible nonequilibrium molecular dynamics simulations typically generate "fractal" [ fractional-dimensional ] phase-space distributions. Because these distributions and their time-reversed twins have zero phase volume, stable attractors "forward in time" and unstable (unobservable) repellors when reversed, these simulations are consistent with the Second Law of Thermodynamics. These same reversibility and stability properties can also be found in compressible Baker Maps, or in their equivalent random walks, motivating their careful study. We illustrate these ideas wit…
Simple time-reversible systems can generate {\it irreversible} flows satisfying the Second Law of Thermodynamics. Maps, and equivalent random walks, can also do this. We study a pair of time-reversible Baker Maps, $N2$ and $N3$, which generate dissipative{\it fractal} phase-space structures. Steadily decreasing phase-space volumes correspond to the dissipation associated with entropy production. Like three smooth reversible dissipative one-body phase-space flows developed in the 1980s and 1990s our maps generate fractal distributions, but in two dimensions rather than three, simplifying visual…
The \$1000 Ian Snook Prize for 2020 will be awarded to the author(s) of the most interesting paper exploring a pair of relatively simple, but fractal, models of nonequilibrium systems, a dissipative time-reversible Baker Map and an equivalent stochastic random walk. The two-dimensional deterministic, time-reversible, chaotic, fractal, and dissipative Baker map is equivalent to the stochastic one-dimensional random walk model for which three distinct estimates for the information dimension, $\{ \ 0.7897,\ 0.741_5, \ 0.7337 \ \}$ have all been put forward. So far there is no cogent explanation f…
The time reversibility characteristic of Hamiltonian mechanics has long been extended to nonHamiltonian dynamical systems modeling nonequilibrium steady states with feedback-based thermostats and ergostats. Typical solutions are multifractal attractor-repellor phase-space pairs with reversed momenta and unchanged coordinates, $(q,p)\longleftrightarrow (q,-p)$ . Weak control of the temperature, $\propto p^2$ and its fluctuation, resulting in ergodicity, has recently been achieved in a three-dimensional time-reversible model of a heat-conducting harmonic oscillator. Two-dimensional cross section…
Aspects of the Nosé and Nosé-Hoover dynamics developed in 1983-1984 along with Dettmann's closely related dynamics of 1996, are considered. We emphasize paradoxes associated with Liouville's Theorem. Our account is pedagogical, focused on the harmonic oscillator for simplicity, though exactly the same ideas can be, and have been, applied to manybody systems. Nosé, Nosé-Hoover, and Dettmann flows were all developed in order to access Gibbs' canonical ensemble directly from molecular dynamics. Unlike Monte Carlo algorithms dynamical flow models are often not ergodic and so can fail to reproduce …
Time-reversible dynamical simulations of nonequilibrium systems exemplify both Loschmidt's and Zermélo's paradoxes. That is, computational time-reversible simulations invariably produce solutions consistent with the {\it irreversible} Second Law of Thermodynamics (Loschmidt's) as well as {\it periodic} in the time (Zermélo's, illustrating Poincaré recurrence). Understanding these paradoxical aspects of time-reversible systems is enhanced here by studying the simplest pair of such model systems. The first is time-reversible, but nevertheless dissipative and periodic, the piecewise-linear compre…
We use nonequilibrium molecular dynamics to analyze and illustrate the qualitative differences between the one-thermostat and two-thermostat versions of equilibrium and nonequilibrium (heat-conducting) harmonic oscillators. Conservative nonconducting regions can coexist with dissipative heat conducting regions in phase space with exactly the same imposed temperature field.
A new discrete time-reversible map of a unit square onto itself is proposed. The map comprises of piecewise linear two-dimensional operations, and is able to represent the macroscopic features of both equilibrium and nonequilibrium dynamical systems. Our operations are analogous to sinusoidally driven shear in the two dimensions, and a radial compression/expansion of a point lying outside/inside a circle centered around origin. Depending upon the radius, the map transitions from being ergodic and nondissipative (like in equilibrium situations) to a limit cycle through intermediate multifractal…
Stochastic Thermodynamics (ST) extends the notions of classical thermodynamics to trajectories taken from a nonequilibrium ensemble. This extension yields a simple approach to fluctuation relations in small systems. Multiple time- and length scales play an important role for measurements but also for the foundations of nonequilibrium statistical mechanics. Here, under the assumptions of local equilibrium we derive the trajectory functionals of ST in the context of reversible deterministic thermostats. Further, the connection to previous work is made.
In this paper we study the statistical properties of a reversible cellular automaton in two out-of-equilibrium settings. In the first part we consider two instances of the initial value problem, corresponding to the inhomogeneous quench and the local quench. Our main result is an exact matrix product expression of the time evolution of the probability distribution, which we use to determine the time evolution of the density profiles analytically. In the second part we study the model on a finite lattice coupled with stochastic boundaries. Once again we derive an exact matrix product expression…
Onsager's phenomenological equations successfully describe irreversible thermodynamic processes. They assume a symmetric coupling matrix between thermodynamic fluxes and forces. It is easily shown that the antisymmetric part of a coupling matrix does not contribute to dissipation. Therefore, entropy production is exclusively governed by the symmetric matrix even in the presence of antisymmetric terms. In this work we focus on the antisymmetric contributions which describe isentropic oscillations and well-defined equations of motion. The formalism contains variables that are equivalent to momen…
Motivated by a recent work on the metabolism of carbohydrates in bacteria, we study the kinetics and thermodynamics of two classic models for reversible polymerization, one preserving the total polymer concentration and the other one not. The chemical kinetics is described by rate equations following the mass-action law. We consider a closed system and nonequilibrium initial conditions and show that the system dynamically evolves towards equilibrium where detailed balance is satisfied. The entropy production during this process can be expressed as the time derivative of a Lyapunov function. Wh…
We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green functions (NEGF). The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit.
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 system to equilibrium free energy differences. In this paper, we derive a generalized version of the fluctuation theorem for stochastic, microscopically reversible dynamics. Invoking this generalized theor…
The relative stability and ergodicity of deterministic time-reversible thermostats, both singly and in coupled pairs, are assessed through their Lyapunov spectra. Five types of thermostat are coupled to one another through a single Hooke's-Law harmonic spring. The resulting dynamics shows that three specific thermostat types, Hoover-Holian, Ju-Bulgac, and Martyna-Klein-Tuckerman, have very similar Lyapunov spectra in their equilibrium four-dimensional phase spaces and when coupled in equilibrium or nonequilibrium pairs. All three of these oscillator-based thermostats are shown to be ergodic, w…
Chemical reaction systems operating in nonequilibrium open-system states arise in a great number of contexts, including the study of living organisms, in which chemical reactions, in general, are far from equilibrium. Here we introduce a theorem that relates forward and re-verse fluxes and free energy for any chemical process operating in a steady state. This rela-tionship, which is a generalization of equilibrium conditions to the case of a chemical process occurring in a nonequilibrium steady state, provides a novel equivalent definition for chemical reaction free energy. In addition, it is …
Nonequilibrium processes occurring in functional materials can significantly impact device efficiencies and are often difficult to characterize due to the broad range of length and time scales involved. In particular, mixed halide hybrid perovskites are promising for optoelectronics, yet the halides reversibly phase separate when photo-excited, significantly altering device performance. By combining nanoscale imaging and multiscale modeling, we elucidate the mechanism underlying this phenomenon, demonstrating that local strain induced by photo-generated polarons promotes halide phase separatio…
In recent work a deterministic and time-reversible boundary thermostat called thermostating by deterministic scattering has been introduced for the periodic Lorentz gas [Phys. Rev. Lett. {\bf 84}, 4268 (2000)]. Here we assess the nonlinear properties of this new dynamical system by numerically calculating its Lyapunov exponents. Based on a revised method for computing Lyapunov exponents, which employs periodic orthonormalization with a constraint, we present results for the Lyapunov exponents and related quantities in equilibrium and nonequilibrium. Finally, we check whether we obtain the same…
Abstract: Models for studying systems in stationary states but out of equilibrium have often empirical nature and very often break the fundamental time reversal symmetry. Here a formal interpretation will be discussed of the widespread idea that, in any event, the particular friction model choice should not matter physically. The proposal is, quite generally, that for the same physical system a time reversible model should be possible. Examples about the Navier-Stokes equations are given.
Large entropy fluctuations in a nonequilibrium steady state of classical mechanics were studied in extensive numerical experiments on a simple 2-freedom model with the so-called Gauss time-reversible thermostat. The local fluctuations (on a set of fixed trajectory segments) from the average heat entropy absorbed in thermostat were found to be non-Gaussian. Approximately, the fluctuations can be discribed by a two-Gaussian distribution with a crossover independent of the segment length and the number of trajectories ('particles'). The distribution itself does depend on both, approaching the sin…
We explore the dynamics of information systems. We show that the driving force for information dynamics is determined by both the information landscape and information flux which determines the equilibrium time reversible and the nonequilibrium time-irreversible behaviours of the system respectively. We further demonstrate that the mutual information rate between the two subsystems can be decomposed into the time-reversible and time-irreversible parts respectively, analogous to the information landscape-flux decomposition for dynamics. Finally, we uncover the intimate relation between the none…
We show for Markov diffusion processes that the quadratic entropic bound, recently derived for the rate functions of nonequilibrium currents, can be seen as being produced by an effective process that creates current fluctuations in a sub-optimal way by modifying only the non-reversible part of the drift or force of the process considered while keeping its reversible part constant. This provides a clear interpretation of the bound in terms of a physical process, which explains, among other things, its relation to the fluctuation relation, linear response, and reversible limits. The existence o…
Framing computation as the transformation of metastable memories, we explore its fundamental thermodynamic limits. The true power of information follows from a novel decomposition of nonequilibrium free energy derived here, which provides a rigorous thermodynamic description of coarse-grained memory systems. In the nearly-quasistatic limit, logically irreversible operations can be performed with thermodynamic reversibility. Yet, here we show that beyond the reversible work Landauer's bound requires of computation, dissipation must be incurred both for modular computation and for neglected stat…
Motivated by recent progresses in nonequilibrium Fluctuation Relations, we present a generalized time reversal for stochastic master equation systems with discrete states that is defined as a splitting of the rate matrix into irreversible and reversible parts. An immediate advantage of this definition is that a variety of fluctuation relations can be attributed to different matrix splitting. Additionally, we also find that, the accustomed total entropy production formula and conditions of the detailed balance must be modified appropriately to account for the presence of the reversible part, wh…
We study the dynamics of the Rule 150 reversible cellular automaton (RCA). This is a one-dimensional lattice system of binary variables with synchronous (Floquet) dynamics, corresponding to a bulk deterministic and reversible discrete version of the kinetically constrained XOR-Fredrickson-Andersen model, whereby the local dynamics is restricted: a site flips if and only if the states of its neighbouring sites are different from each other. Like other RCA which have been studied recently, such as Rule 54 and Rule 201, Rule 150 is integrable, however, in contrast is noninteracting. In particular…
We give a proof of transient fluctuation relations for the entropy production (dissipation function) in nonequilibrium systems, which is valid for most time reversible dynamics. We then consider the conditions under which a transient fluctuation relation yields a steady state fluctuation relation for driven nonequilibrium systems whose transients relax, producing a unique nonequilibrium steady state. Although the necessary and sufficient conditions for the production of a unique nonequilibrium steady state are unknown, if such a steady state exists, the generation of the steady state fluctuati…
It will be shown, how the Boltzmannian ideas on statistical physics can be naturally applied to nonequilibrium thermodynamics. A similar approach for treating nonequilibrium phenomena has been successfully used by Einstein and Smoluchowski treating fluctuations. It will be argued, that due to the reversibility of the microscopic equations, all processes - also macroscopic ones - must at least in principle be reversible. Also, a clear conceptual distinction between equilibrium and nonequilibrium states is not possible in the Boltzmannian framework, which is just the reason why these concepts sh…
Fluctuation theorems, which have been developed over the past 15 years, have resulted in fundamental breakthroughs in our understanding of how irreversibility emerges from reversible dynamics, and have provided new statistical mechanical relationships for free energy changes. They describe the statistical fluctuations in time-averaged properties of many-particle systems such as fluids driven to nonequilibrium states, and provide some of the very few analytical expressions that describe nonequilibrium states. Quantitative predictions on fluctuations in small systems that are monitored over shor…
Biological systems use energy to maintain non-equilibrium distributions for long times, e.g. of chemical concentrations or protein conformations. What are the fundamental limits of the power used to "hold" a stochastic system in a desired distribution over states? We study the setting of an uncontrolled Markov chain $Q$ altered into a controlled chain $P$ having a desired stationary distribution. Thermodynamics considerations lead to an appropriately defined Kullback-Leibler (KL) divergence rate $D(P||Q)$ as the cost of control, a setting introduced by Todorov, corresponding to a Markov decisi…
The Fluctuation Theorems are a group of exact relations that remain valid irrespective of how far the system has been driven away from equilibrium. Other than having practical applications, like determination of equilibrium free energy change from nonequilibrium processes, they help in our understanding of the Second Law and the emergence of irreversibility from time-reversible equations of motion at microscopic level. A vast number of such theorems have been proposed in literature, ranging from Hamiltonian to stochastic systems, from systems in steady state to those in transient regime, and f…
Enyzme kinetics are cyclic. We study a Markov renewal process model of single-enzyme turnover in nonequilibrium steady-state (NESS) with sustained concentrations for substrates and products. We show that the forward and backward cycle times have idential non-exponential distributions: $\QQ_+(t)=\QQ_-(t)$. This equation generalizes the Haldane relation in reversible enzyme kinetics. In terms of the probabilities for the forward ($p_+$) and backward ($p_-$) cycles, $k_BT\ln(p_+/p_-)$ is shown to be the chemical driving force of the NESS, $Δμ$. More interestingly, the moment generating function o…
Explaining the emergence of stochastic irreversible macroscopic dynamics from time-reversible deterministic microscopic dynamics is one of the key problems in philosophy of physics. The Mori-Zwanzig projection operator formalism, which is one of the most important methods of modern nonequilibrium statistical mechanics, allows for a systematic derivation of irreversible transport equations from reversible microdynamics and thus provides a useful framework for understanding this issue. However, discussions of the Mori-Zwanzig formalism in philosophy of physics tend to focus on simple variants ra…