All current formulations of nonequilibrium thermodynamics of open chemical reaction networks rely on the assumption of non-interacting species. We develop a general theory which accounts for interactions between chemical species within a mean-field approach using activity coefficients. Thermodynamic consistency requires that rate equations do not obey to standard mass-action kinetics, but account for the interactions with concentration dependent kinetic constants. Many features of the ideal formulations are recovered. Crucially, the thermodynamic potential and the forces driving non-ideal chemical systems out of equilibrium are identified. Our theory is general and holds for any mean-field expression of the interactions leading to lower bounded free energies.
We build a rigorous nonequilibrium thermodynamic description for open chemical reaction networks of elementary reactions. Their dynamics is described by deterministic rate equations satisfying mass action law. Our most general framework considers open networks driven by time-dependent chemostats. The energy and entropy balances are established and a nonequilibrium Gibbs free energy is introduced. The difference between this latter and its equilibrium form represents the minimal work done by the chemostats to bring the network in its nonequilibrium state. It is minimized in nondriven detailed-b…
The thermodynamics is studied with the thermodynamic parameter of the lifetime, first-passage time, generalizing the equilibrium thermodynamics. Various ways of describing several stationary nonequilibrium states in the system are considered. The possibilities of increasing the lifetime of the system under external influences on it are investigated.
A thermodynamic expression for the analog of the canonical ensemble for nonequilibrium systems is described based on a purely information theoretical interpretation of entropy. As an application, it is shown that this nonequilibrium canonical distribution implies some important results from nonequilibrium thermodynamics, specifically, the fluctuation theorem and the Jarzynski-equality.
Aspects of the modern dynamical systems approach to thermodynamics of stationary states out of equilibrium with attention to the original conceptions which arose at the beginnings of Statistical Mechanics
A variant of continuous nonequilibrium thermodynamic theory based on the postulate of the scale invariance of the local relation between generalized fluxes and forces has been proposed. This single postulate replaces the assumptions on local equilibrium and on the known relation between thermodynamic fluxes and forces, which are widely used in classical nonequilibrium thermodynamics. It has been shown that such a modification not only makes it possible to deductively obtain the main results of classical linear nonequilibrium thermodynamics, but also provides a number of statements for a nonlin…
Chemical reaction networks (CRNs) are prototypical complex systems because reactions are nonlinear and connected in intricate ways, and they are also essential to understand living systems. Here, I discuss how recent developments in nonequilibrium thermodynamics provide new insight on how CRNs process energy and perform sophisticated tasks, and describe open challenges in the field.
Nonequilibrium work-Hamiltonian connection for a microstate plays a central role in diverse branches of statistical thermodynamics (fluctuation theorems, quantum thermodynamics, stochastic thermodynamics, etc.). We show that the change in the Hamiltonian for a microstate should be identified with the work done by it, and not the work done on it. This contradicts the current practice in the field. The difference represents a contribution whose average gives the work that is dissipated due to irreversibility. As the latter has been overlooked, the current identification does not properly account…
To describe the nonequilibrium states of the system, a new thermodynamic parameter - system lifetime - is introduced. Statistical distributions that describe the behavior of energy and lifetime are recorded. Entropy and obtained thermodynamic relations are compared with the results of Extended Irreversible thermodynamics, where as an additional parameter selected fluxes. For the case of thermal conductivity explicit expressions are obtained for average lifetime and conjugate thermodynamic quantity. It is shown that near the equilibrium state, when is only one stationary nonequilibrium state, f…
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.
Development of thermodynamic induction up to second order gives a dynamical bifurcation for thermodynamic variables and allows for the prediction and detailed explanation of nonequilibrium phase transitions with associated spontaneous symmetry breaking. By taking into account nonequilibrium fluctuations, long range order is analyzed for possible pattern formation. Consolidation of results up to second order produces thermodynamic potentials that are maximized by stationary states of the system of interest. These new potentials differ from the traditional thermodynamic potentials. In particular…
The relation between thermostats of "isoenergetic" and "frictionless" kind is studied and their equivalence in the thermodynamic limit is proved in space dimension $d=1,2$ and, for special geometries, $d=3$.
Master equation could be applied to model various kinds of biochemical systems. A general theory for its time-dependent nonequilibrium thermodynamics is rigorously derived. We not only introduce a concept of general internal energy, but also propose an extension of the equilibrium state. Moreover, we find out an explicit expression for the extended form of the Second Law, which is phenomenologically stated as "the conversion of work to excess heat is irreversible". The theory is carefully applied to several thermodynamic processes, and its consistence with the classical thermodynamics is clear…
We compare two approaches to nonequilibrium thermodynamics, the two-generator bracket formulation of time-evolution equations for averages and the macroscopic fluctuation theory, for an isothermal driven diffusive system under steady state conditions. The fluctuation dissipation relations of both approaches play an important role for a detailed comparison. The nonequilibrium Helmholtz free energies introduced in these two approaches differ as a result of boundary conditions. A Fokker-Planck equation derived by projection operator techniques properly reproduces long range fluctuations in nonequ…
Current formulations of nonequilibrium thermodynamics of open chemical reaction networks only consider chemostats as free-energy sources sustaining nonequilibrium behaviours. Here, we extend the theory to include incoherent light as a source of free energy. We do so by relying on a local equilibrium assumption to derive the chemical potential of photons relative to the system they interact with. This allows us to identify the thermodynamic potential and the thermodynamic forces driving light-reacting chemical systems out of equilibrium. We use this framework to treat two paradigmatic photochem…
We show that systems driven by an external force and described by Nose-Hoover dynamics allow for a consistent nonequilibrium thermodynamics description when the thermostatted variable is initially assumed in a state of canonical equilibrium. By treating the "real" variables as the system and the thermostatted variable as the reservoir, we establish the first and second law of thermodynamics. As for Hamiltonian systems, the entropy production can be expressed as a relative entropy measuring the system-reservoir correlations established during the dynamics.
Comparison of extended irreversible thermodynamics and nonequilibrium statistical operator method with thermodynamics based on a distribution containing the first-passage time
In this work, we analyze the nonequilibrium thermodynamics of a class of neural networks known as Restricted Boltzmann Machines (RBMs) in the context of unsupervised learning. We show how the network is described as a discrete Markov process and how the detailed balance condition and the Maxwell-Boltzmann equilibrium distribution are sufficient conditions for a complete thermodynamics description, including nonequilibrium fluctuation theorems. Numerical simulations in a fully trained RBM are performed and the heat exchange fluctuation theorem is verified with excellent agreement to the theory.…
In previous papers we have introduced a natural nonequilibrium free energy by considering the functional describing the large fluctuations of stationary nonequilibrium states. While in equilibrium this functional is always convex, in nonequilibrium this is not necessarily the case. We show that in nonequilibrium a new type of singularities can appear that are interpreted as phase transitions. In particular, this phenomenon occurs for the one-dimensional boundary driven weakly asymmetric exclusion process when the drift due to the external field is opposite to the one due to the external reserv…
How can we derive the evolution equations of dissipative systems? What is the relation between the different approaches? How much do we understand the fundamental aspects of a second law based framework? Is there a hierarchy of dissipative and ideal theories at all? How far can we reach with the new methods of nonequilibrium thermodynamics?
A general nonequilibrium thermodynamic theory is developed for time-dependent Langevin dynamics, starting from the common definition of nonequilibrium Gibbs entropy. It is shown that the notations appearing in the First and the Second Law of thermodynamics could be consistently applied to transient nonequilibrium processes. We find out a general equality representing the energy balance relation for the system, and further an explicit mathematical interpretation for the extended form of the Second Law is proposed, which only comes into existence in the time-dependent case. More applications to …
We examine the effects of the Dzyaloshinsky-Moriya (DM) interaction on the nonequilibrium thermodynamics in an anisotropic $XY$ spin chain, which is driven out of equilibrium by a sudden quench of the control parameter of the Hamiltonian. By analytically evaluating the statistical properties of the work distribution and the irreversible entropy production, we investigate the influences of the DM interaction on the nonequilibrium thermodynamics of the system with different parameters at various temperatures. We find that depending on the anisotropy of the system and the temperature, the DM inte…
An alternative approach - nonequilibrium evolution thermodynamics, is compared with classical Landau approach. A statistical justification of the approach is carried out with help of probability distribution function on an example of a solid with vacancies. Two kinds of kinetic equations are deduced in terms of the internal energy and the modified free energy.
We analyze the static response to perturbations of nonequilibrium steady states that can be modeled as one-dimensional diffusions on the circle. We demonstrate that an arbitrary perturbation can be broken up into a combination of three specific classes of perturbations that can be fruitfully addressed individually. For each class, we derive a simple formula that quantitatively characterizes the response in terms of the strength of nonequilibrium driving valid arbitrarily far from equilibrium.
In a recent paper [P. Strasberg and M. Esposito, Phys. Rev. E {\bf 101}, 050101(R) (2020)] an attempt is presented to formulate the nonequilibrium thermodynamics of an open system in terms of the Hamiltonian of mean force. The purpose of the present comment is to clarify severe restrictions of this approach and also to stress that recently noted ambiguities [P. Talkner and P. Hänggi, Phys. Rev. E {\bf 94}, 022143 (2016)] of fluctuating thermodynamic potentials cannot be removed in the suggested way.
We review theory of information thermodynamics which incorporates effects of measurement and feedback into nonequilibrium thermodynamics of a small system, and discuss how the second law of thermodynamics should be extended for such situations. We address the issue of the maximum work that can be extracted from the system in the presence of a feedback controller (Maxwell's demon) and provide a few illustrative examples. We also review a recent experiment that realized a Maxwell's demon based on a feedback-controlled ratchet.
We establish a general theory of feedback control on classical stochastic thermodynamic systems, and generalize nonequilibrium equalities such as the fluctuation theorem and the Jarzynski equality in the presence of feedback control with multiple measurements. Our results are generalizations of the previous relevant works to the situations with general measurements and multi-heat baths. The obtained equalities involve additional terms that characterize the information obtained by measurements or the efficacy of feedback control. A generalized Szilard engine and a feedback-controlled ratchet ar…
To describe the nonequilibrium states of a system we introduce a new thermodynamic parameter - the lifetime of a system. The statistical distributions which can be obtained out of the mesoscopic description characterizing the behaviour of a system by specifying the stochastic processes are written down. The expressions for the nonequilibrium entropy, temperature and entropy production are obtained, which at small values of fluxes coincide with those derived within the frame of extended irreversible thermodynamics. The expressions generalizing the Maxwell-Cattaneo relations of extended irrevers…
The Jarzynski relation is a recently discovered result relating the average exponential of the work done under nonequilibrium conditions to an equilibrium free energy difference. We illustrate this remarkable relation by considering the expansion and compression of a classical ideal gas particle inside a cavity with a moving piston in one dimension. Using a simple relationship between the distributions of the nonequilibrium work done in the two (forward and reverse) processes, we verify the Jarzynski relation and discuss the practical realization of the Jarzynski equality for the model.
The second law of ordinary thermodynamics and the second law of steady state thermodynamics, as proposed by Oono and Paniconi, are investigated from the microscopic point of view for the open quantum system. Based on the H-theorem of Lindblad, we show that both second laws are consistent with the quantum dynamics generated by the completely positive map. In addition, microscopic expressions of entropy production and ``housekeeping heat'' are obtained for some classes of dynamical quantum systems.
We explore driven lattice gases for the existence of an intensive thermodynamic variable which could determine "equilibration" between two nonequilibrium steady-state systems kept in weak contact. In simulations, we find that these systems satisfy surprisingly simple thermodynamic laws, such as the zero-th law and the fluctuation-response relation between the particle-number fluctuation and the corresponding susceptibility remarkably well. However at higher densities, small but observable deviations from these laws occur due to nontrivial contact dynamics and the presence of long-range spatial…
We develop the stochastic approach to thermodynamics based on the stochastic dynamics, which can be discrete (master equation) continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second, the definition of entropy production rate which is nonnegative and vanishes in thermodynamic equilibrium. Based on these assumptions we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium, and how the macroscopic laws are derived from the stochastic dynamics. These studies inc…
We give nonequilibrium Green's function (NEGF) perspective on thermodynamics formulations for open quantum systems strongly coupled to baths. Scattering approach implying thermodynamic consideration of a super-system (system plus baths) weakly coupled to external super-baths is compared with consideration of thermodynamics of a system strongly coupled to its baths. We analyze both approaches from the NEGF perspective and argue that the latter yields a possibility of thermodynamic formulation consistent with dynamical (quantum transport) description.
We here present the complete analysis of experiments on driven Brownian motion and electric noise in a $RC$ circuit, showing that thermodynamic entropy production can be related to the breaking of time-reversal symmetry in the statistical description of these nonequilibrium systems. The symmetry breaking can be expressed in terms of dynamical entropies per unit time, one for the forward process and the other for the time-reversed process. These entropies per unit time characterize dynamical randomness, i.e., temporal disorder, in time series of the nonequilibrium fluctuations. Their difference…
This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with $N$ species, $M$ reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemistry kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy functi…
The typicality of the canonical state shows that majority of the states are indistinguishable from equilibrium, and thus the nonequilibrium states are exceptionally rare in the extremely high-dimensional Hilbert space. On the contrary, we can easily apply an external force acting on the system, and then the actual density matrix quantitatively deviates from the canonical state specified by the system Hamiltonian at each instance. To express how the external forcing amounts to the deviation from equilibrium, we give a universal thermodynamic expression of the lower bound of Hilbert-Schmidt dist…
We propose a tensor-network algorithm for discrete-time stochastic dynamics of a homogeneous system in the thermodynamic limit. We map a $d$-dimensional nonequilibrium Markov process to a $(d+1)$-dimensional infinite tensor network by using a higher-order singular-value decomposition. As an application of the algorithm, we compute the nonequilibrium relaxation from a fully magnetized state to equilibrium of the one- and two- dimensional Ising models with periodic boundary conditions. Utilizing the translational invariance of the systems, we analyze the behavior in the thermodynamic limit direc…
A Unified Nonequilibrium Framework: Thermodynamic Distance, Dissipation, and Stationary Laws via Effective State Count, Variational Stationarity, and Thermodynamic Bounds
We show that a nominal temperature can be consistently and uniquely defined everywhere in the phase diagram of large classes of nonequilibrium kinetic Ising spin models. In addition, we confirm the recent proposal that, at critical points, the large-time ``fluctuation-dissipation ratio'' $X_\infty$ is a universal amplitude ratio and find in particular $X_\infty \approx 0.33(2)$ and $X_\infty = 1/2$ for the magnetization in, respectively, the two-dimensional Ising and voter universality classes.
We show that intensive thermodynamic parameters associated to additive conserved quantities can be naturally defined from a statistical approach in far-from-equilibrium steady-state systems, under few assumptions, and without any detailed balance requirement. It may apply, e.g., to dissipative systems like granular gases where volume or mass is still conserved, or to systems with periodic boundary conditions where fluxes of conserved quantities are present. We emphasize the usefulness of this concept to characterize the coexistence of different nonequilibrium phases, and discuss the influence …
We investigate the open dynamics of a chain of interacting spins using the quantized version of the GENERIC equation from classical out-of-equilibrium thermodynamics. We focus on both equilibrium and nonequilibrium scenarios for chains of different sizes. While in the equilibrium case we demonstrate thermal equilibration to the correct many-body Gibbs density matrix, in the nonequilibrium dynamics we show a ballistic-to-diffusive transition in the steady-state energy current and a scaling that is consistent with Fourier's law of heat transfer.
Thermodynamic uncertainty principles make up one of the few rare anchors in the largely uncharted waters of nonequilibrium systems, the fluctuation theorems being the more familiar. In this work we aim to trace the uncertainties of thermodynamic quantities in nonequilibrium systems to their quantum origins, namely, to the quantum uncertainty principles. Our results enable us to make this categorical statement: For Gaussian systems, thermodynamic functions are functionals of the Robertson-Schrodinger uncertainty function, which is always non-negative for quantum systems, but not necessarily so …
Development of steady state thermodynamics and statistical mechanics depends crucially on our ability to develop notions of equilibrium thermodynamics for nonequilibrium steady states (NESS). The present paper considers the development of heat capacity. A modified definition is proposed which continues to maintain the same relation to steady state Shannon entropy as in equilibrium, thus providing a thermodynamically consistent treatment of NESS heat capacity.
We generalize an idea in the works of Landauer and Bennett on computations, and Hill's in chemical kinetics, to emphasize the importance of kinetic cycles in mesoscopic nonequilibrium thermodynamics (NET). For continuous stochastic systems, a NET in phase space is formulated in terms of cycle affinity $\nabla\wedge\big(\mathbf{D}^{-1}\mathbf{b}\big)$ and vorticity potential $\mathbf{A}(\mathbf{x})$ of the stationary flux $\mathbf{J}^{*}=\nabla\times\mathbf{A}$. Each bivectorial cycle couples two transport processes represented by vectors and gives rise to Onsager's reciprocality; the scalar pr…
The standard formulation of tunneling transport rests on an open-boundary modeling. There, conserving approximations to nonequilibrium Green function or quantum-statistical mechanics provide consistent but computational costly approaches; alternatively, use of density-dependent ballistic-transport calculations [e.g., Phys. Rev. B 52, 5335 (1995)], here denoted `DBT', provide computationally efficient (approximate) atomistic characterizations of the electron behavior but has until now lacked a formal justification. This paper presents an exact, variational nonequilibrium thermodynamic theory fo…
The interactions of tiny objects with their environment are dominated by thermal fluctuations. Guided by theory and assisted by micromanipulation tools, scientists have begun to study such interactions in detail.
Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager's reciprocal relations in this c…
We extend Jarzynski's work relation and the second law of thermodynamics to a heat conducting system which is operated by an external agent. These extensions contain a new non equilibrium contribution expressed as the violation of the (linear) response relation caused by the operation. We find that a natural extension of the minimum work principle involves information about the time-reversed operation, and is far from straightforward. Our work relation may be tested experimentally especially when the temperature gradient is small.
We present an approach based on a density matrix expansion to study thermodynamic properties of a quantum system strongly coupled to two or more baths. For slow external driving of the system, we identify the adiabatic and nonadiabatic contributions to thermodynamic quantities, and we show how the first and second laws of thermodynamics are manifested in the strong coupling regime. Particularly, we show that the entropy production is positive up to second order in the driving speed. The formulation can be applied both for Bosonic and Fermionic systems, and recovers previous results for the equ…
Using an additivity property, we study particle-number fluctuations in a system of interacting self-propelled particles, called active Brownian particles (ABPs), which consists of repulsive disks with random self-propulsion velocities. From a fluctuation-response relation - a direct consequence of additivity, we formulate a thermodynamic theory which captures the previously observed features of nonequilibrium phase transition in the ABPs from a homogeneous fluid phase to an inhomogeneous phase of coexisting gas and liquid. We substantiate the predictions of additivity by analytically calculati…
A model of coupled molecular oscillators is proposed to study nonequilibrium thermodynamics of synchronization. We find that synchronization of nonequilibrium oscillators costs energy even when the oscillator-oscillator coupling is conservative. By solving the steady state of the many-body system analytically, we show that the system goes through a nonequilibrium phase transition driven by energy dissipation, and the critical energy dissipation depends on both the frequency and strength of the exchange reactions. Moreover, our study reveals the optimal design for achieving maximum synchronizat…
We use the work done on and the heat removed from a system to maintain it in a nonequilibrium steady state for a thermodynamic-like description of such a system as well as of its fluctuations. Based on a generalized Onsager-Machlup theory for nonequilibrium steady states we indicate two ambiguities, not present in an equilibrium state, in defining such work and heat: one due to a non-uniqueness of time-reversal procedures and another due to multiple possibilities to separate heat into work and an energy difference in nonequilibrium steady states. As a consequence, for such systems, the work an…
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 another 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 s…
Dissipative effects in electromagnetism on macroscopic scales are examined by coarse graining the microscopic Maxwell equations with respect to time. We illustrate a procedure to derive the dissipative effects on the macroscopic scale by using a Green-Kubo type expression in terms of the microscopic fluctuations and the correlations between them. The resulting macroscopic Maxwell equations are formulated within the General Equation for the Non-Equilibrium Reversible-Irreversible Coupling (GENERIC) framework, accounting also for inhomogeneous temperature.
