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The macroscopic hydrodynamic equations are derived for many-body systems in the local-equilibrium approach, using the Schr\"odinger picture of quantum mechanics. In this approach, statistical operators are defined in terms of microscopic densities associated with the fundamentally conserved quantities and other slow modes possibly emerging from continuous symmetry breaking, as well as macrofields conjugated to these densities. Functional identities can be deduced, allowing us to identify the reversible and dissipative parts of the mean current densities, to obtain general equations for the time evolution of the conjugate macrofields, and to establish the relationship to projection-operator methods. The entropy production is shown to be nonnegative by applying the Peierls-Bogoliubov inequality to a quantum integral fluctuation theorem. Using the expansion in the gradients of the conjugate macrofields, the transport coefficients are given by Green-Kubo formulas and the entropy production rate can be expressed in terms of quantum Einstein-Helfand formulas, implying its nonnegativity in agreement with the second law of thermodynamics. The results apply to multicomponent fluids and can be extended to condensed matter phases with broken continuous symmetries.

This book provides a comprehensive and self-contained overview of recent progress in nonequilibrium statistical mechanics, in particular, the discovery of fluctuation relations and other time-reversal symmetry relations. The significance of these advances is that nonequilibrium statistical physics is no longer restricted to the linear regimes close to equilibrium, but extends to fully nonlinear regimes. These important new results have inspired the development of a unifying framework for describing both the microscopic dynamics of collections of particles, and the macroscopic hydrodynamics and thermodynamics of matter itself. The book discusses the significance of this theoretical framework in relation to a broad range of nonequilibrium processes, from the nanoscale to the macroscale, and is essential reading for researchers and graduate students in statistical physics, theoretical chemistry and biological physics.

Education actors in the United States are increasingly promoting language skills development of our students. The Seal of Biliteracy (SoBL) has grown into a popular initiative to promote biliteracy and recognize students who demonstrate skills in English and another language. However, the language used to promote biliteracy and the criteria put in place to award the SoBL risk exacerbating differences in opportunities between linguistic communities rather than promote speakers of all languages. Minnesota introduced the SoBL through a law explicitly aimed at supporting education for English language learners. This paper critically reviews the goals of the SoBL initiative, describes the approaches Minnesota has taken to support English language learners to earn the seal and discusses the practical challenges schools and districts face. States and districts need to explicitly address these barriers to avoid increasing inequities through the SoBL.

The aim of the current study is to expand our understanding of cross-linguistic transfer (CLT) to new languages and settings under-represented in the research literature. Empirical evidence of CLT ...

This paper estimates the short-term, partial-equilibrium impacts of a public-private partnership program for low-cost private secondary schools in Uganda. The public-private partnership program is part of a broader strategy to absorb large increases in secondary enrollment following the introduction of universal secondary education. Under the program, the government offers a per-student subsidy to participating private schools. Program implementation allowed for a randomized phase-in study design to estimate the causal impacts of the program on private school performance. The study finds that the public-private partnership program helped absorb large numbers of eligible students in secondary schools. Student performance in participating private schools was significantly better than in nonparticipating private schools. The study finds that improved student performance is potentially linked to increased input availability, as well as positive selection of government aided students in private schools. Suggestive evidence indicates that this selection most likely occurs on the part of households rather than schools.

Homochirality, i.e. the dominance across all living matter of one enantiomer over the other among chiral molecules, is thought to be a key step in the emergence of life. Building on ideas put forward by Frank and many others, we proposed recently one such mechanism in Laurentet al.(Laurent, 2021Proc. Natl Acad. Sci. USA118, e2012741118. (doi:10.1073/pnas.2012741118)) based on the properties of large out of equilibrium chemical networks. We showed that in such networks, a phase transition towards a homochiral state is likely to occur as the number of chiral species in the system becomes large or as the amount of free energy injected into the system increases. This paper aims at clarifying some important points in that scenario, not covered by our previous work. We first analyse the various conventions used to measure chirality, introduce the notion of chiral symmetry of a network and study its implications regarding the relative chiral signs adopted by different groups of molecules. We then propose a generalization of Frank’s model for large chemical networks, which we characterize completely using methods of random matrices. This analysis is extended to sparse networks, which shows that the emergence of homochirality is a robust transition.

International audience; The selection of a single molecular handedness, or homochirality across all living matter, is a mystery in the origin of life. Frank's seminal model showed in the fifties how chiral symmetry breaking can occur in non-equilibrium chemical networks. However, an important shortcoming in this classic model is that it considers a small number of species, while there is no reason for the prebiotic system, in which homochirality first appeared, to have had such a simple composition. Furthermore, this model does not provide information on what could have been the size of the molecules involved in this homochiral prebiotic system. Here, we show that large molecular systems are likely to undergo a phase transition towards a homochiral state, as a consequence of the fact that they contain a large number of chiral species. Using chemoinformatics tools, we quantify how abundant are chiral species in the chemical universe of all possible molecules of a given length. Then, we propose that Frank's model should be extended to include a large number of species, in order to possess the transition towards homochirality as confirmed by numerical simulations. Finally, using random matrix theory, we prove that large non-equilibrium reaction networks possess a generic and robust phase transition towards a homochiral state.

For the statistics of currents in quantum transport, microreversibility is shown to provide a way to obtain the statistical cumulants at the order n+1 from the measurement of the cumulants at the order n or lower. This fundamental result is based on relations generalizing the fluctuation-dissipation theorem and the Onsager-Casimir reciprocal relations from linear toward nonlinear transport properties, as a consequence of the time-reversal symmetry of the underlying microscopic Hamiltonian dynamics. The method is demonstrated in detail in the case of multiterminal Aharonov-Bohm rings. Within the independent electron approximation, the cumulant generating function, which fully specifies the statistics of the nonequilibrium currents, is obtained from the scattering matrix of these circuits. The time-reversal symmetry relations are explicitly shown to express the cumulants at equilibrium up to the fourth order in terms of lower-order cumulants and their nonequilibrium responses in the presence of an external magnetic field.

The paper by Malek Mansour and Garcia [Phys. Rev. E 101, 052135 (2020)2470-004510.1103/PhysRevE.101.052135] is shown to be based on misconceptions in the stochastic formulation of chemical thermodynamics in reactive systems. Their erroneous claims, asserting that entropy production cannot be correctly evaluated using path probabilities whenever the reactive system involves more than one elementary reaction leading to the same composition changes, are refuted.

A unified set of hydrodynamic equations describing condensed phases of matter with broken continuous symmetries is derived using a generalization of the statistical-mechanical approach based on the local equilibrium distribution. The dissipativeless and dissipative parts of the current densities and the entropy production are systematically deduced in this approach by expanding in powers of the gradients of the macrofields. Green–Kubo formulas are obtained for all the linear transport coefficients. The consequences of microreversibility and spatial symmetries are investigated, leading to the prediction of cross effects resulting from Onsager–Casimir reciprocal relations. Crystalline solids and liquid crystals are potential examples of application. The approach is clarifying the links between the microscopic Hamiltonian dynamics and the thermodynamic and transport properties at the macroscale.

Active matter, comprising many active agents interacting and moving in fluids or more complex environments, is a commonly occurring state of matter in biological and physical systems. By its very nature, active matter systems exist in nonequilibrium states. In this paper, the active agents are small Janus colloidal particles that use chemical energy provided by chemical reactions occurring on their surfaces for propulsion through a diffusiophoretic mechanism. As a result of interactions among these colloids, either directly or through fluid velocity and concentration fields, they may act collectively to form structures such as dynamic clusters. A general nonequilibrium thermodynamics framework for the description of such systems is presented that accounts for both self-diffusiophoresis and diffusiophoresis due to external concentration gradients, and is consistent with microreversibility. It predicts the existence of a reciprocal effect of diffusiophoresis back onto the reaction rate for the entire collection of colloids in the system, as well as the existence of a clustering instability that leads to nonequilibrium inhomogeneous system states., SCOPUS: ar.j, info:eu-repo/semantics/published

Methods are presented to evaluate the entropy production rate in stochastic reactive systems. These methods are shown to be consistent with known results from nonequilibrium chemical thermodynamics. Moreover, it is proved that the time average of the entropy production rate can be decomposed into the contributions of the cycles obtained from the stoichiometric matrix in both stochastic processes and deterministic systems. These methods are applied to a complex reaction network constructed on the basis of Roessler's reinjection principle and featuring chemical chaos.

Langevin equations for the self-thermophoretic dynamics of Janus motors partially coated with an absorbing layer that is heated by a radiation field are presented. The derivation of these equations is based on fluctuating hydrodynamics and radiative heat transfer theory involving stochastic equations for bulk phases and surface processes that are consistent with microscopic reversibility. Expressions for the self-thermophoretic force and torque for arbitrary slip boundary conditions are obtained. The overdamped Langevin equations for the colloid displacement and radiative heat transfer provide expressions for the self-thermophoretic velocity and its reciprocal contribution where an external force can influence the radiative heat transfer. A nonequilibrium fluctuation formula is also derived and shows how the probability density of the Janus particle displacement and radiation energy transfer during the time interval [0,t] are related to the mechanical and thermal affinities that characterize the nonequilibrium system state.

The local equilibrium approach previously developed by the authors (J Mabillard and P Gaspard 2020 J. Stat. Mech. 103203) for matter with broken symmetries is applied to crystalline solids. The macroscopic hydrodynamics of crystals and their local thermodynamic and transport properties are deduced from the microscopic Hamiltonian dynamics. In particular, the Green–Kubo formulas are obtained for all the transport coefficients. The eight hydrodynamic modes and their dispersion relation are studied for general and cubic crystals. In the same twenty crystallographic classes as those compatible with piezoelectricity, cross effects coupling transport between linear momentum and heat or crystalline order are shown to split the degeneracy of damping rates for modes propagating in opposite generic directions.

The kinetics and thermodynamics of free living copolymerization are studied for processes with rates depending on k monomeric units of the macromolecular chain behind the unit that is attached or detached. In this case, the sequence of monomeric units in the growing copolymer is a kth-order Markov chain. In the regime of steady growth, the statistical properties of the sequence are determined analytically in terms of the attachment and detachment rates. In this way, the mean growth velocity as well as the thermodynamic entropy production and the sequence disorder can be calculated systematically. These different properties are also investigated in the regime of depolymerization where the macromolecular chain is dissolved by the surrounding solution. In this regime, the entropy production is shown to satisfy Landauer's principle.

Multivariate fluctuation relations are established in several stochastic models of transistors, which are electronic devices with three ports and thus two coupled currents. For all these models, the transport properties are shown to satisfy Onsager’s reciprocal relations in the linear regime close to equilibrium as well as their generalizations holding in the nonlinear regimes farther away from equilibrium, as a consequence of microreversibility. In the first model, which is related to the Ebers–Moll transport model for bipolar junction transistors, there is no internal state variable and particle exchanges between the ports are described as a Markov jump process with constant rates. In the second model, the rates linearly depend on an internal random variable, representing the occupancy of the transistor by charge carriers. The third model has rates nonlinearly depending on the internal occupancy, as in single-electron transistors. For the first and second models, finite-time multivariate fluctuation relations are also established, giving insight into the convergence towards the asymptotic form of multivariate fluctuation relations in the long-time limit.

A nonequilibrium fluctuation theorem is established for a colloidal particle driven by an external force within the hydrodynamic theory of Brownian motion, describing hydrodynamic memory effects such as the t^(-3/2) power-law decay of the velocity autocorrelation function. The generalized Langevin equation is obtained for the general case of slip boundary conditions between the particle and the fluid. The Gaussian probability distributions for the particle to evolve in position-velocity space are deduced. It is proved that the joint probability distributions of forward and time-reversed paths have a ratio depending only on the work performed by the external force and the fluid temperature, in spite of the nonMarkovian character of the generalized Langevin process., Dedicated to the memory of Christian Van den Broeck

The theory of multistate template-directed reversible copolymerization is developed by extending the method based on iterated function systems to matrices, taking into account the possibility of multiple activation states instead of a single one for the growth process. In this extended theory, the mean growth velocity is obtained with an iterated matrix function system and the probabilities of copolymer sequences are given by matrix products defined along the template. The theory allows us to understand the effects of template heterogeneity, which include a fractal distribution of local growth velocities far enough from equilibrium, and a regime of sublinear growth in time close to equilibrium.

Microreversibility constrains the fluctuations of the nonequilibrium currents that cross an open system. This can be seen from the so-called fluctuation relations, which are a direct consequence of microreversibility. Indeed, the latter are known to impose time-reversal symmetry relations on the statistical cumulants of the currents and their responses at arbitrary orders in the deviations from equilibrium. Remarkably, such relations have been recently analyzed by means of Euler's polynomials. Here we show that fluctuation relations can actually be explicitly written in terms of the constant terms of these particular polynomials. We hence demonstrate that Euler's polynomials are indeed fundamentally rooted in fluctuation relations, both in the absence and the presence of an external magnetic field., 10 pages

We present a stochastic approach for charge transport in transistors. In this approach, the electron and hole densities are governed by diffusion-reaction stochastic differential equations satisfying local detailed balance and the electric field is determined with the Poisson equation. The approach is consistent with the laws of electricity, thermodynamics, and microreversibility. In this way, the signal amplifying effect of transistors is verified under their working conditions. We also perform the full counting statistics of the two electric currents coupled together in transistors and we show that the fluctuation theorem holds for their joint probability distribution. Similar results are obtained including the displacement currents. In addition, the Onsager reciprocal relations and their generalizations to nonlinear transport properties deduced from the fluctuation theorem are numerically shown to be satisfied.

Colloidal motors with micrometer dimensions and no moving parts can be propelled by self-diffusiophoresis. Coupling between molecular concentration gradients generated by asymmetric surface chemical reactions and the velocity slip between colloidal particle and the surrounding fluid solution is responsible for propulsion. The interfacial properties involved in this propulsion mechanism can be described by nonequilibrium thermodynamics and statistical mechanics, disclosing the fundamental role of microreversibility in the coupling between motion and reaction. Among other phenomena, the approach predicts that propulsion by fuel consumption has the reciprocal effect of fuel synthesis by mechanical action.

We studied the catalytic NO2(g) + H2(g)/Pt system on model platinum catalysts with nanoscale spatial resolution by means of field emission microscopy (FEM). While the surface of the catalyst is in a non-reactive state at low H2 partial pressure, bursts of activity are observed when increasing this parameter. These kinetic instabilities subsequently evolve towards self-sustained periodic oscillations for a wide range of pressures. Combining time series analyses and numerical simulations of a simple reaction model, we clarify how these observations fit in the traditional classification of dynamical systems. In particular, reconstructions of the probability density around oscillating trajectories show that the experimental system defines a crater-like structure in probability space. The experimental observations thus correspond to a noise-perturbed limit cycle emerging from a nanometric reactive system. This conclusion is further supported by comparison with stochastic simulations of the proposed chemical model. The obtained results and simulations pave the way towards a better understanding of reactive nanosystems.

A finite-time fluctuation theorem is proved for the diffusion-influenced surface reaction AB in a domain with any geometry where the species A and B undergo diffusive transport between the reservoir and the catalytic surface. A corresponding finite-time thermodynamic force or affinity is associated with the symmetry of the fluctuation theorem. The time dependence of the affinity and the reaction rates characterizing the stochastic process can be expressed analytically in terms of the solution of deterministic diffusion equations with specific boundary conditions.

A stochastic approach for charge transport in diodes is developed in consistency with the laws of electricity, thermodynamics, and microreversibility. In this approach, the electron and hole densities are ruled by diffusion-reaction stochastic partial differential equations and the electric field generated by the charges is determined with the Poisson equation. These equations are discretized in space for the numerical simulations of the mean density profiles, the mean electric potential, and the current-voltage characteristics. Moreover, the full counting statistics of the carrier current and the measured total current including the contribution of the displacement current are investigated. On the basis of local detailed balance, the fluctuation theorem is shown to hold for both currents.

Kinetic theory and thermodynamics of reaction networks are extended to the out-of-equilibrium dynamics of continuous-flow stirred tank reactors (CSTR) and serial transfers. On the basis of their stoichiometry matrix, the conservation laws and the cycles of the network are determined for both dynamics. It is shown that the CSTR and serial transfer dynamics are equivalent in the limit where the time interval between the transfers tends to zero proportionally to the ratio of the fractions of fresh to transferred solutions. These results are illustrated with finite cross-catalytic reaction network and an infinite reaction network describing mass exchange between polymers. Serial transfer dynamics is typically used in molecular evolution experiments in the context of research on the origins of life. The present study is shedding a new light on the role played by serial transfer parameters in these experiments., 11 pages, 7 figures

The propulsion of active particles by self-diffusiophoresis is driven by asymmetric catalytic reactions on the particle surface that generate a mechanochemical coupling between the fluid velocity and the concentration fields of fuel and product in the surrounding solution. Because of thermal and molecular fluctuations in the solution, the motion of micrometric or submicrometric active particles is stochastic. Coupled Langevin equations describing the translation, rotation, and reaction of such active particles are deduced from fluctuating chemohydrodynamics and fluctuating boundary conditions at the interface between the fluid and the particle. These equations are consistent with microreversibility and the Onsager-Casimir reciprocal relations between affinities and currents, and provide a thermodynamically consistent basis for the investigation of the dynamics of active particles propelled by diffusiophoretic mechanisms.

Janus motors with chemically active and inactive hemispheres can operate only under nonequilibrium conditions where detailed balance is broken by fluxes of chemical species that establish a nonequilibrium state. A microscopic model for reversible reactive collisions on a Janus motor surface is constructed and shown to satisfy detailed balance. The model is used to study Janus particle reactive dynamics in systems at equilibrium where generalized chemical rate laws that include time-dependent rate coefficients with power-law behavior are shown to describe reaction rates. While maintaining reversible reactions on the Janus catalytic hemisphere, the system is then driven into a nonequilibrium steady state by fluxes of chemical species that control the chemical affinity. The statistical properties of the self-propelled Janus motor in this nonequilibrium steady state are investigated and compared with the predictions of a fluctuating thermodynamics theory. The model has utility beyond the examples presented here, since it allows one to explore various aspects of nonequilibrium fluctuations in systems with self-diffusiophoretic motors from a microscopic perspective.

Nonequilibrium interfacial thermodynamics is formulated in the presence of surface reactions for the study of diffusiophoresis in isothermal systems. As a consequence of microreversibility and Onsager-Casimir reciprocal relations, diffusiophoresis, i.e., the coupling of the tangential components of the pressure tensor to the concentration gradients of solute species, has a reciprocal effect where the interfacial currents of solutes are coupled to the slip velocity. The presence of surface reactions is shown to modify the diffusiophoretic and reciprocal effects at the fluid-solid interface. The thin-layer approximation is used to describe the solution flowing near a reactive solid interface. Analytic formulas describing the diffusiophoretic and reciprocal effects are deduced in the thin-layer approximation and tested numerically for the Poiseuille flow of a solution between catalytic planar surfaces.

The thermodynamics of copolymerization processes leading to the formation and replication of copolymers is presented. Copolymers are natural one-dimensional supports of information, which may be coded in the sequence of monomeric units randomly attached or detached during their synthesis. Multivariate fluctuation relations are here established for copolymerization processes synthesizing Bernoulli and first-order Markov chains. Thereof, the thermodynamic entropy production is deduced and shown to depend on quantities characterizing information possibly stored in the copolymer sequence.

Scattering theory is complemented by recent results on full counting statistics, the multivariate fluctuation relation for currents, and time asymmetry in temporal disorder characterized by the Connes-Narnhofer-Thirring entropy per unit time, in order to establish relationships with the thermodynamics of quantum transport. Fluctuations in the bosonic or fermionic currents flowing across an open system in contact with particle reservoirs are described by their cumulant generating function, which obeys the multivariate fluctuation relation as the consequence of microreversibility. Time asymmetry in temporal disorder is shown to manifest itself out of equilibrium in the difference between a time-reversed coentropy and the Connes-Narnhofer-Thirring entropy per unit time. This difference is shown to be equal to the thermodynamic entropy production for ideal quantum gases of bosons and fermions. The results are illustrated for a two-terminal circuit.

The kinetic equations of DNA replication are shown to be exactly solved in terms of iterated function systems, running along the template sequence and giving the statistical properties of the copy sequences, as well as the kinetic and thermodynamic properties of the replication process. With this method, different effects due to sequence heterogeneity can be studied, in particular, a transition between linear and sublinear growths in time of the copies, and a transition between continuous and fractal distributions of the local velocities of the DNA polymerase along the template. The method is applied to the human mitochondrial DNA polymerase $\ensuremath{\gamma}$ without and with exonuclease proofreading.

The reversible kinetics of copolymerization is solved analytically for the multistate mechanism proposed by B. D. Coleman and T. G. Fox [J. Chem. Phys. 38, 1065 (1963)] under low conversion conditions where the concentrations of monomeric species are chemostatted and stay constant in time. Although the rates of this mechanism only depends on the currently attached or detached monomer, the growing macromolecular chain forms a nonMarkovian sequence that is characterized by matrices associated with every monomeric unit composing the sequence. These matrices are obtained by solving the kinetic equations and they determine the growth velocity of the copolymers, the statistical properties of its possible sequences, as well as the thermodynamics of the copolymerization process.

The single-particle and collective dynamics of systems comprising Janus motors, solvent, and reactive solute species maintained in nonequilibrium states are investigated. Reversible catalytic reactions with the solute species take place on the catalytic faces of the motors, and the nonequilibrium states are established either by imposing constant-concentration reservoirs that feed and remove reactive species or through out-of-equilibrium fluid phase reactions. We consider general intermolecular interactions between the Janus motor hemispheres and the reactive species. For single motors, we show that the reaction rate depends nonlinearly on an applied external force when the system is displaced far from equilibrium. We also show that a finite-time fluctuation formula derived for fixed catalytic particles describes the nonequilibrium reactive fluctuations of moving Janus motors. Simulation of the collective dynamics of small ensembles of Janus motors with reversible kinetics under nonequilibrium conditions is carried out, and the spatial and orientational correlations of dynamic cluster states are discussed. The conditions leading to the instability of the homogeneous motor distribution and the onset of nonequilibrium dynamical clustering are described.

We propose a mechanism by which dynamical randomness may appear in many-body systems without sensitivity to initial conditions. We characterize dynamical randomness using the Kolmogorov-Sinai (KS) entropy per unit time and its 1987 quantum extension by Connes, Narnhofer, and Thirring (CNT). In this respect, quantum systems fall into (at least) two large classes: (1) few-body bounded systems with discrete energy spectra whose entropy per unit time is vanishing; and (2) many-body open systems of statistical mechanics with continuous energy spectra whose entropy per unit time may be positive, like ideal gases and beams of particles. We calculate the classical and quantum entropies per unit time of the ideal gases and show that they are positive and in correspondence. Moreover, we show that the KS entropy per unit time is recovered from the CNT entropy per unit time using a decomposition suggested by the works of Griffiths, Gell-Mann, Hartle, and Omnes on quantum histories. We also discuss about the relationships between the quantum histories, the exponential decay of some n-time correlation functions, repeated measurements, and the CNT entropy per unit time.

An overview is given of recent advances in the nonequilibrium statistical mechanics of quantum systems and, especially, of the time-reversal symmetry relations that have been discovered in this context. The systems considered are driven out of equilibrium by time-dependent forces or by coupling to large reservoirs of particles and energy. The symmetry relations are established for the exchange of energy and particles between the subsystem and its environment. These results have important consequences. In particular, generalizations of the Kubo formula and the Casimir-Onsager reciprocity relations can be deduced beyond linear response properties. Applications to electron quantum transport in mesoscopic semiconducting circuits are discussed. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA.