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The notion of temperature in out-of-equilibrium systems is still elusive. Here, we explore three different temperature definitions for an athermal tracer immersed in a out-of-equilibrium bath of active Brownian particles, with which it interacts solely through collisions. Temperatures are, respectively, defined from velocity fluctuations, the fluctuation-dissipation theorem and a heat fluctuation theorem, and we find their values to increase with the tracer’s mass following sigmoidal trends, the first two sharing similar values, the one defined from the fluctuation theorem showing lower ones. Notably, these trends are reminiscent of the trend of the kinetic temperature of a single free active particle as function of its mass. Using thus the latter as fit functional form, we interpret the tracer as effectively behaving like a single free active particle with the same mass but lower persistence time or activity amplitude. [ABSTRACT FROM AUTHOR]

In addition to providing general constraints on probability distributions, fluctuation theorems allow us to infer essential information on the role played by temperature in heat exchange phenomena. In this numerical study, we measure the temperature of an out-of-equilibrium active bath using a fluctuation theorem that relates the fluctuations in the heat exchanged between two baths to their temperatures. Our setup consists of a single particle moving between two wells of a quartic potential accommodating two different baths. The heat exchanged between the two baths is monitored according to two definitions: as the kinetic energy carried by the particle whenever it jumps from one well to the other and as the work performed by the particle on one of the two baths when immersed in it. First, we consider two equilibrium baths at two different temperatures and verify that a fluctuation theorem featuring the baths temperatures holds for both heat definitions. Then, we introduce an additional Gaussian coloured noise in one of the baths, so as to make it effectively an active (out-of-equilibrium) bath. We find that a fluctuation theorem is still satisfied with both heat definitions. Interestingly, in this case the temperature obtained through the fluctuation theorem for the active bath corresponds to the kinetic temperature when considering the first heat definition, while it is larger with the second one. We interpret these results by looking at the particle jump phenomenology. [ABSTRACT FROM AUTHOR]

Recent advancements in information thermodynamics have revealed that information can be directly converted into mechanical work. Specifically, RNA transcription and nanopore sequencing serve as prime examples of this conversion, by reading information from a DNA template. This paper introduces an information thermodynamic model in which these molecular motors can move along the DNA template by converting the information read from the template DNA into their own motion. This process is a stochastic one, characterized by significant fluctuations in forward movement and is described by the Fokker–Planck equation, based on drift velocity and diffusion coefficients. In the current study, it is hypothesized that by utilizing the sequence information of the template DNA as mutual information, the fluctuations can be reduced, thereby biasing the forward movement on DNA and, consequently, reducing reading errors. Further research into the conversion of biological information by molecular motors could unveil new applications, insights, and important findings regarding the characteristics of information processing in biology. [ABSTRACT FROM AUTHOR]

The adaptive and surprising emergent properties of biological materials self-assembled in far-from-equilibrium environments serve as an inspiration for efforts to design nanomaterials. In particular, controlling the conditions of self-assembly can modulate material properties, but there is no systematic understanding of either how to parameterize external control or how controllable a given material can be. Here, we demonstrate that branched actin networks can be encoded with metamaterial properties by dynamically controlling the applied force under which they grow and that the protocols can be selected using multi-task reinforcement learning. These actin networks have tunable responses over a large dynamic range depending on the chosen external protocol, providing a pathway to encoding "memory" within these structures. Interestingly, we obtain a bound that relates the dissipation rate and the rate of "encoding" that gives insight into the constraints on control--both physical and information theoretical. Taken together, these results emphasize the utility and necessity of nonequilibrium control for designing self-assembled nanostructures. [ABSTRACT FROM AUTHOR]

The plastic deformation of almost all solid polymers can be represented by a thermally activated rate process involving the motion of cooperative mobile elements over potential barriers, based on the Eyring activated rate theory. The present study shows that the governing equations for the Eyring rate theory can be completely derived based on the principle of microscopic reversibility in the framework of non-equilibrium dynamics. [ABSTRACT FROM AUTHOR]

Complex systems can convert energy imparted by nonequilibrium forces to regulate how quickly they transition between long-lived states. While such behavior is ubiquitous in natural and synthetic systems, currently there is no general framework to relate the enhancement of a transition rate to the energy dissipated or to bound the enhancement achievable for a given energy expenditure. We employ recent advances in stochastic thermodynamics to build such a framework, which can be used to gain mechanistic insight into transitions far from equilibrium. We show that under general conditions, there is a basic speed limit relating the typical excess heat dissipated throughout a transition and the rate amplification achievable. We illustrate this tradeoff in canonical examples of diffusive barrier crossings in systems driven with autonomous and deterministic external forcing protocols. In both cases, we find that our speed limit tightly constrains the rate enhancement.

The review provides a pedagogical but comprehensive introduction to the foundations of a recently proposed statistical mechanics (μ NEQT) of a stable nonequilibrium thermodynamic body, which may be either isolated or interacting. It is an extension of the well-established equilibrium statistical mechanics by considering microstates m k in an extended state space in which macrostates (obtained by ensemble averaging A ^ ) are uniquely specified so they share many properties of stable equilibrium macrostates. The extension requires an appropriate extended state space, three distinct infinitessimals d α = (d , d e , d i) operating on various quantities q during a process, and the concept of reduction. The mechanical process quantities (no stochasticity) like macrowork are given by A ^ d α q , but the stochastic quantities C ^ α q like macroheat emerge from the commutator C ^ α of d α and A ^ . Under the very common assumptions of quasi-additivity and quasi-independence, exchange microquantities d e q k such as exchange microwork and microheat become nonfluctuating over m k as will be explained, a fact that does not seem to have been appreciated so far in diverse branches of modern statistical thermodynamics (fluctuation theorems, quantum thermodynamics, stochastic thermodynamics, etc.) that all use exchange quantities. In contrast, dq k and d i q k are always fluctuating. There is no analog of the first law for a microstate as the latter is a purely mechanical construct. The second law emerges as a consequence of the stability of the system, and cannot be violated unless stability is abandoned. There is also an important thermodynamic identity  d i Q ≡ d i W   ≥   0 with important physical implications as it generalizes the well-known result of Count Rumford and the Gouy-Stodola theorem of classical thermodynamics. The μ NEQT has far-reaching consequences with new results, and presents a new understanding of thermodynamics even of an isolated system at the microstate level, which has been an unsolved problem. We end the review by applying it to three different problems of fundamental interest. [ABSTRACT FROM AUTHOR]

We establish a fluctuation theorem for an open quantum bipartite system that explicitly manifests the role played by quantum correlation. Generally quantum correlations may substantially modify the universality of classical thermodynamic relations in composite systems. Our fluctuation theorem finds a non-equilibrium parameter of genuinely quantum nature that sheds light on the emerging quantum information thermodynamics. Specifically we show that the statistics of quantum correlation fluctuation obtained in a time-reversed process can provide a useful insight into addressing work and heat in the resulting thermodynamic evolution. We illustrate these quantum thermodynamic relations by two examples of quantum correlated systems. [ABSTRACT FROM AUTHOR]

Understanding the function of rotary molecular motors, such as rotary ATPases, relies on our ability to visualize single-molecule rotation. Traditional imaging methods often involve tagging those motors with nanoparticles (NPs) and inferring their rotation from the translational motion of NPs. Here, we report an approach using "two-faced" Janus NPs to directly image the rotation of a single V-ATPase from Enterococcus hirae , an ATP-driven rotary ion pump. By employing a 500 nm silica/gold Janus NP, we exploit its asymmetric optical contrast, a silica core with a gold cap on one hemisphere, to achieve precise imaging of the unidirectional counterclockwise rotation of single V-ATPase motors immobilized on surfaces. Despite the added viscous load from the relatively large Janus NP probe, our approach provides accurate torque measurements of a single V-ATPase. This study underscores the advantages of Janus NPs over conventional probes, establishing them as powerful tools for the single-molecule analysis of rotary molecular motors.

A new type of symmetry in the large deviation function of a time-integrated current is introduced. This current is different from the fluctuating entropy production for which the large deviation function is symmetric in the content of the fluctuation theorem. The origin of this symmetry, similar to that of the Gallavotti-Cohen-Evans-Morriss symmetry, is related to time-reversal. The symmetry is more unveiled when one performs an appropriate grouping of stochastic trajectories in the space of microscopic configurations. It turns out that the characteristic polynomial of the modified generator of this current is not symmetric; however, its minimum eigenvalue is symmetric.

Maintained by environmental fluxes, biological systems are thermodynamic processes that operate far from equilibrium without detailed-balanced dynamics. Yet, they often exhibit well defined nonequilibrium steady states (NESSs). More importantly, critical thermodynamic functionality arises directly from transitions among their NESSs, driven by environmental switching. Here, we identify the constraints on excess heat and dissipated work necessary to control a system that is kept far from equilibrium by background, uncontrolled “housekeeping” forces. We do this by extending the Crooks fluctuation theorem to transitions among NESSs, without invoking an unphysical dual dynamics. This and corresponding integral fluctuation theorems determine how much work must be expended when controlling systems maintained far from equilibrium. This generalizes thermodynamic feedback control theory, showing that Maxwellian Demons can leverage mesoscopic-state information to take advantage of the excess energetics in NESS transitions. We also generalize an approach recently used to determine the work dissipated when driving between functionally relevant configurations of an active energy-consuming complex system. Altogether, these results highlight universal thermodynamic laws that apply to the accessible degrees of freedom within the effective dynamic at any emergent level of hierarchical organization. By way of illustration, we analyze a voltage-gated sodium ion channel whose molecular conformational dynamics play a critical functional role in propagating action potentials in mammalian neuronal membranes.

Understanding the origin of irreversibility in thermodynamics has been a fundamental scientific challenge and puzzle for nearly a century. Initially, the discussions related to classical thermodynamic systems, but recently quantum systems became the main focus. Explanations have often been sought by reference to classical equations of motion, which are time-reversible. We conjecture that the origin of irreversibility lies in energy dissipation, a term that is at the core of the Second Law of thermodynamics. However, thermodynamic irreversibility is distinct from time-irreversibility. A system in thermodynamic equilibrium may have reached this state via a deterministic, integrable and therefore time-reversible process, or, alternatively, via an irreversible route, both resulting in thermodynamically indistinguishable states. The process with time-reversible history may become irreversible by a process called thermalization, which occurs when the system loses memory of its history without the necessity of energy dissipation. Quantum systems do this by losing phase coherence; for classical systems the decoherence is at zero frequency, due to loss of time correlation. More generally, not only equilibrium systems may have lost memory of their history. A common cause of memory loss is probabilistic/stochastic events, which are not deterministic and take place only with a certain probability at any given time. In contrast to thermalization, equilibration involves energy dissipation within a system or to the surroundings or by decrease of concentration of the system. Time-reversibility is not related to system size, and the fluctuation theorem is a probabilistic and not a deterministic phenomenon and therefore not suited to provide an understanding of the irreversibility of time in thermodynamic systems. There are also processes which are both dissipative and probabilistic, such as the radiative or non-radiative decay of electronically excited states. Dissipation of a given energy into multiple smaller energy quanta (heat) is by itself not fully reversible for kinetic reasons. It is kinetically a first-order probabilistic process, whereas the reverse is a second- or higher-order process. Thermodynamics provides empirical laws, developed for conventional matter as we know it on planet Earth and in our laboratories. Of relevance here is the Second Law, also called the arrow of time, stating that spontaneous processes take place for isolated systems with increasing entropy. It is assumed to hold also for the universe as a whole. However, over the distances of individual galaxies, self-gravitation leads to conditions where the kinetic energy of the system decreases while the total energy increases, pretending negative heat capacity, and it allows the formation of black holes. This requires an extension of the Second Law. This review aims at presenting an overarching tutorial clarification of the subject. [Display omitted] [ABSTRACT FROM AUTHOR]

This paper investigates generalized thermodynamic relationships in physical systems where relevant macroscopic variables are determined by the exponential Kolmogorov–Nagumo average. We show that while the thermodynamic entropy of such systems is naturally described by Rényi’s entropy with parameter γ , an ordinary Boltzmann distribution still describes their statistics under equilibrium thermodynamics. Our results show that systems described by exponential Kolmogorov–Nagumo averages can be interpreted as systems originally in thermal equilibrium with a heat reservoir with inverse temperature β that are suddenly quenched to another heat reservoir with inverse temperature $\beta^{^{\prime}} = (1-\gamma)\beta$ . Furthermore, we show the connection with multifractal thermodynamics. For the non-equilibrium case, we show that the dynamics of systems described by exponential Kolmogorov–Nagumo averages still observe a second law of thermodynamics and the H-theorem. We further discuss the applications of stochastic thermodynamics in those systems—namely, the validity of fluctuation theorems—and the connection with thermodynamic length.

Novel hidden thermodynamic structures have recently been uncovered during the investigation of nonequilibrium thermodynamics for multiscale stochastic processes. Here we reveal the martingale structure for a general thermodynamic functional of inhomogeneous singularly perturbed diffusion processes under second-order averaging, where a general thermodynamic functional is defined as the logarithmic Radon–Nykodim derivative between the laws of the original process and a comparable process (forward case) or its time reversal (backward case). In the forward case, we prove that the regular and anomalous parts of a thermodynamic functional are orthogonal martingales. In the backward case, while the regular part may not be a martingale, we prove that the anomalous part is still a martingale. With the aid of the martingale structure, we prove the integral fluctuation theorem satisfied by the regular and anomalous parts of a general thermodynamic functional. Further extensions and applications to stochastic thermodynamics are also discussed, including the martingale structure and fluctuation theorems for the regular and anomalous parts of entropy production and housekeeping heat in the absence or presence of odd variables. [ABSTRACT FROM AUTHOR]

We derive the fluctuation theorem for a stochastic and periodically driven system coupled to two reservoirs with the aid of a master equation. We write down the cumulant generating functions for both the current and entropy production in closed compact forms so as to treat the adiabatic and nonadiabatic contributions systematically. We derive the fluctuation theorem by taking into account the time reversal symmetry and the property that the instantaneous currents flowing into the left and the right reservoir are not equal. It is found that the fluctuation–dissipation relation derived from the fluctuation theorem involves an expansion with respect to the time derivative of the affinity. [ABSTRACT FROM AUTHOR]

Spontaneous violations of the Clausius–Duhem (CD) inequality in Couette-type collisional flows of model granular media are studied. Planar systems of monosized circular discs (with disc numbers from 10 to 204, and disc diameters from 0.001 m to 1 m) with frictional-Hookean contacts are simulated under periodic boundary conditions by a molecular dynamics. The scale-dependent homogenization of micropolar media is used to determine the energy balances and mechanical entropy production. The dissipation function exhibits spontaneous negative entropy increments described by the fluctuation theorem. The boundary between violations and non-violations of the CD inequality is mapped in the parameter space, where the probability of such events diminishes with the disc diameter, the disc number and the area fraction increasing. The dissipation function is a random process, tending to Gaussian as the number of discs increases, and possessing non-trivial fractal and anti-persistent Hurst properties. [ABSTRACT FROM AUTHOR]

Turbulent flows are out-of-equilibrium because the energy supply at large scales and its dissipation by viscosity at small scales create a net transfer of energy among all scales. This energy cascade is modelled by approximating the spectral energy balance with a nonlinear Fokker–Planck equation consistent with accepted phenomenological theories of turbulence. The steady-state contributions of the drift and diffusion in the corresponding Langevin equation, combined with the killing term associated with the dissipation, induce a stochastic energy transfer across wavenumbers. The fluctuation theorem is shown to describe the scale-wise statistics of forward and backward energy transfer and their connection to irreversibility and entropy production. The ensuing turbulence entropy is used to formulate an extended turbulence thermodynamics. [ABSTRACT FROM AUTHOR]

Asymptotic fluctuation theorems are statements of a Gallavotti-Cohen symmetry in the rate function of either the time-averaged entropy production or heat dissipation of a process. Such theorems have been proved for various general classes of continuous-time deterministic and stochastic processes, but always under the assumption that the forces driving the system are time independent, and often relying on the existence of a limiting ergodic distribution. In this paper we extend the asymptotic fluctuation theorem for the first time to inhomogeneous continuous-time processes without a stationary distribution, considering specifically a finite state Markov chain driven by periodic transition rates. We find that for both entropy production and heat dissipation, the usual Gallavotti-Cohen symmetry of the rate function is generalized to an analogous relation between the rate functions of the original process and its corresponding backward process, in which the trajectory and the driving protocol have been time-reversed. The effect is that spontaneous positive fluctuations in the long time average of each quantity in the forward process are exponentially more likely than spontaneous negative fluctuations in the backward process, and vice-versa, revealing that the distributions of fluctuations in universes in which time moves forward and backward are related. As an additional result, the asymptotic time-averaged entropy production is obtained as the integral of a periodic entropy production rate that generalizes the constant rate pertaining to homogeneous dynamics.

We apply tensor networks to counting statistics for the stochastic particle transport in an out-of-equilibrium diffusive system. This system is composed of a one-dimensional channel in contact with two particle reservoirs at the ends. Two tensor-network algorithms, namely, density matrix renormalization group and time evolving block decimation, are respectively implemented. The cumulant generating function for the current is numerically calculated and then compared with the analytical solution. Excellent agreement is found, manifesting the validity of these approaches in such an application. Moreover, the fluctuation theorem for the current is shown to hold.

We establish the Level-1 and Level-3 Large Deviation Principles (LDPs) for invariant measures on shift spaces over finite alphabets under very general decoupling conditions for which the thermodynamic formalism does not apply. Such decoupling conditions arise naturally in multifractal analysis, in Gibbs states with hard-core interactions, and in the statistics of repeated quantum measurement processes. We also prove the LDP for the entropy production of pairs of such measures and derive the related Fluctuation Relation. The proofs are based on Ruelle–Lanford functions, and the exposition is essentially self-contained. [ABSTRACT FROM AUTHOR]

As a central concept in fluid dynamics stability is fundamental in understanding transitions from laminar to turbulent flow. In continuum flows, it is well-established that a transition to turbulence can occur at subcritical Reynolds numbers, in contrast to theoretical predictions. In non-equilibrium molecular dynamics (NEMD), it has been widely observed that at a critical Reynolds number the fluid undergoes an ordering transition from an amorphous phase to a 'string' phase. Using the fluctuation theorem (FT) and the dissipation function, we generalize the classical continuum Reynolds-Orr equation to sheared molecular fluids by ascribing a natural description to the nature of stochastic perturbations, i.e. fluctuations in shear stress. Via the Poincaré inequality, we arrive at a new stability criterion by providing a lower bound on the exponential decay of perturbations, which reduces to the classical continuum result in the limit of infinite system size. We investigate the nature of these velocity perturbations and conditions necessary for growth in the kinetic energy of perturbations. We obtain a fluid dependent estimate for the critical Reynolds number by which one may estimate the critical Reynolds number at which the fluid transitions to the string phase, thus providing a framework for generalizing classical continuum theories to the microscale. [ABSTRACT FROM AUTHOR]

Entropy fluctuations with time occur in finite-sized time-evolving dissipative systems. There is a need to comprehend the role of these fluctuations on the fluctuations-averaged entropy generation rate, over a large enough observation time interval. In this non-equilibrium thermodynamic investigation, the Fluctuation Theorem (FT) and Principle of Least Action are re-visited to articulate their implications for dissipative systems. The Principle of Maximum Entropy Production (MaxEP: the entropy generation rate of a dissipative system is maximized by paths of least action) is conceptually identified as the Principle of Least Action for dissipative systems. A Thermodynamic Fusion Theorem that merges the FT and the MaxEP is introduced for addressing the role of fluctuations in entropy production. It identifies "entropy fluctuations" as the "least-action path" for maximizing the time-averaged entropy production in a dissipative system. The validity of this introduced theorem is demonstrated for the case of entropy fluctuations in Rayleigh–Taylor flow instability. [ABSTRACT FROM AUTHOR]

In this paper, we study Jarzynski's equality and fluctuation theorems for diffusion processes. While some of the results considered in the current work are known in the (mainly physics) literature, we review and generalize these nonequilibrium theorems using mathematical arguments, therefore enabling further investigations in the mathematical community. On the numerical side, variance reduction approaches such as importance sampling method are studied in order to compute free energy differences based on Jarzynski's equality. [ABSTRACT FROM AUTHOR]

Abstract Tracking the Brownian motion of aerosol particles as they settle in air allows a mass measurement. The particle typically falls downward at its terminal settling velocity; however, the particle occasionally will be displaced upwards due to Brownian fluctuations. The number of occurrences of upward and downward fluctuations is compared, using the formula for the work fluctuation theorem, to yield the mass. This method can be applied to either a single particle or a collection of particles. The advantages of this method include no required information about the size, shape, or density of the particle. Details of the analysis method are presented and illustrated with experimental data. Highlights • Tracking the Brownian motion of particles settling in air allows a mass measurement. • A falling particle is occasionally displaced upwards. • Occurrences of upward and downward displacements depend on a particle's mass. • The formula used is the work fluctuation theorem. • Advantages include no requirement for data on particle's size, shape, or density. [ABSTRACT FROM AUTHOR]

We provide a complete derivation of hydrodynamic equations for nonrelativistic systems based on quantum field theories of spinless Schrödeinger fields, assuming that an initial density operator takes a special form of the local Gibbs distribution. The constructed optimized/renormalized perturbation theory for real-time evolution enables us to separately evaluate dissipative and nondissipative parts of constitutive relations. It is shown that the path-integral formula for local thermal equilibrium together with the symmetry properties of the resulting action—the nonrelativistic diffeomorphism and gauge symmetry in the thermally emergent Newton-Cartan geometry—provides a systematic way to derive the nondissipative part of constitutive relations. We further show that dissipative parts are accompanied with the entropy production operator together with two kinds of fluctuation theorems by the use of which we derive the dissipative part of constitutive relations and the second law of thermodynamics. After obtaining the exact expression for constitutive relations, we perform the derivative expansion and derive the first-order hydrodynamic (Navier-Stokes) equation with the Green-Kubo formula for transport coefficients. [ABSTRACT FROM AUTHOR]

We extend stochastic thermodynamics by relaxing the two assumptions that the Markovian dynamics must be linear and that the equilibrium distribution must be a Boltzmann distribution. We show that if we require the second law to hold when those assumptions are relaxed, then it cannot be formulated in terms of Shannon entropy. However, thermodynamic consistency is salvaged if we reformulate the second law in terms of generalized entropy; our first result is an equation relating the precise form of the non-linear master equation to the precise associated generalized entropy which results in thermodynamic consistency. We then build on this result to extend the usual trajectory-level definitions of thermodynamic quantities that are appropriate even when the two assumptions are relaxed. We end by using these trajectory-level definitions to derive extended versions of the Crooks fluctuation theorem and Jarzynski equality which apply when the two assumptions are relaxed.

Nonlinear non-equilibrium thermodynamic relations have been constructed based on the generalized Ehrenfest−Klein model. Using these relations, the behavior of the entropy and its production in time at arbitrary deviations from equilibrium has been studied. It has been shown that the transient fluctuation theorem is valid for this model if a dissipation functional is treated as the thermodynamic entropy production.

A colloidal particle immersed in a bath of bacteria is a typical example of a passive particle in an active bath. To model this, we take an overdamped harmonically trapped particle subjected to a thermal and a non-equilibrium noise arising from the active bath. The harmonic well can be attributed to a laser trap or to the small amplitude motion of the sedimented colloid at the bottom of the capillary. In the long time, the system reaches a non-equilibrium steady state that can be described by an effective temperature. Here we investigate whether fluctuation relations for entropy hold in the presence of Gaussian active noise. In addition, when subjected to a deterministic time dependent drag, we find that transient fluctuation theorem for work cannot be applied in conventional form. However, a steady state fluctuation relation for work emerges out with a renormalized temperature. [ABSTRACT FROM AUTHOR]

The fluctuation theorem is a representative theorem in non-equilibrium statistical physics actively studied in the 1990s. Relating to entropy production in non-equilibrium states, the theorem has been used to estimate the driving power of motor proteins from fluctuation in their motion. In this review, usage of the fluctuation theorem in experiments on motor proteins is illustrated for biologists, especially those who study mechanobiology, in which force measurement is a central issue. We first introduce the application of the fluctuation theorem in measuring the rotary torque of the rotary motor protein F1-ATPase. Next, as an extension of this application, a recent trial estimating the force generated during cargo transport in vivo by the microtubule motors kinesin and dynein is introduced. Elucidation of the physical mechanism of such transport is important, especially for neurons, in which deficits in cargo transport are deeply related to neuronal diseases. Finally, perspectives on the fluctuation theorem as a new technique in the field of neuroscience are discussed. [ABSTRACT FROM AUTHOR]

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 for both open and closed quantum systems. In this article, we discuss about a few such relations, when the system evolves under Hamiltonian dynamics. [ABSTRACT FROM AUTHOR]

In this work, we discussed the stochastic thermodynamics of mesoscopic electron transfer reactions between ions and electrodes. With a relationship between the reaction rate constant and the electrode potential, we find that the heat dissipation βq equals to the dynamic irreversibility of the reaction system minus an internal entropy change term. The total entropy change Δst is defined as the summation of the system entropy change Δs and the heat dissipation βq such that Δst=Δs+βq. Even though the heat dissipation depends linearly on the electrode potential, the total entropy change is found to satisfy the fluctuation theorem -Δst>=1, and hence a second law-like inequality reads <Δst>≥0. Our study provides a practical methodology for the stochastic thermodynamics of electrochemical reactions, which may find applications in biochemical and electrochemical reaction systems. [ABSTRACT FROM AUTHOR]