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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.

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.

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.

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 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.

We present a systematic computation of the heat conductivity of the Markov jump process modeling the energy exchanges in an array of locally confined hard spheres at the conduction threshold. Based on a variational formula [Sasada M. 2016, {\it Thermal conductivity for stochastic energy exchange models}, arXiv:1611.08866], explicit upper bounds on the conductivity are derived, which exhibit a rapid power-law convergence towards an asymptotic value. We thereby conclude that the ratio of the heat conductivity to the energy exchange frequency deviates from its static contribution by a small negative correction, its dynamic contribution, evaluated to be $-0.000\,373$ in dimensionless units. This prediction is corroborated by kinetic Monte Carlo simulations which were substantially improved compared to earlier results., 33 pages, minor revisions

A kinetic theory is developed for exonuclease-deficient DNA polymerases, based on the experimental observation that the rates depend not only on the newly incorporated nucleotide, but also on the previous one, leading to the growth of Markovian DNA sequences from a Bernoullian template. The dependences on nucleotide concentrations and template sequence are explicitly taken into account. In this framework, the kinetic and thermodynamic properties of DNA replication, in particular, the mean growth velocity, the error probability, and the entropy production in terms of the rate constants and the concentrations are calculated analytically. Theory is compared with numerical simulations for the DNA polymerases of T7 viruses and human mitochondria., Comment: Physical Review E (2016)

For open systems subjected to external magnetic fields, relations between the statistical cumulants of their fluctuating currents and their response coefficients are established at arbitrary orders in the deviations from equilibrium, as a consequence of microreversibility. These relations are systematically deduced from the extension of the fluctuation relation for this class of systems, and analyzed by using methods developed in [M. Barbier and P. Gaspard, J. Phys. A: Math. Theor. 51 (2018) 355001]. We unambiguously identify, among the statistical cumulants and their nonequilibrium responses, which of these quantities are independent and thus left unspecified by the fluctuation relation, i.e. by microreversibility. We also find the explicit expression of the dependent quantities in terms of the independent ones by means of coefficients of Euler polynomials., Comment: 30 pages

A finite-time fluctuation theorem for the diffusion-influenced surface reaction A B is investigated for spherical and Janus catalytic particles. The finite-time rates and thermodynamic force are analytically calculated by solving diffusion equations with the special boundary conditions of the finite-time fluctuation theorem. Theory is compared with numerical simulations carried out with two different methods: a random walk algorithm and multiparticle collision dynamics.

Microreversibility rules the fluctuations of the currents flowing across open systems in nonequilibrium (or equilibrium) steady states. As a consequence, the statistical cumulants of the currents and their response coefficients at arbitrary orders in the deviations from equilibrium obey time-reversal symmetry relations. It is shown that these relations allow us to systematically reduce the amount of independent quantities that need to be measured experimentally or computed theoretically in order to fully characterize the linear and nonlinear transport properties of general open systems. This reduction is shown to approach one half for quantities of arbitrarily high orders., Comment: 31 pages

We derive a set of isometric fluctuation relations, which constrain the order parameter fluctuations in finite-size systems at equilibrium and in the presence of a broken symmetry. These relations are exact and should apply generally to many condensed-matter physics systems. Here, we establish these relations for magnetic systems and nematic liquid crystals in a symmetry-breaking external field, and we illustrate them on the Curie-Weiss and the XY models. Our relations also have implications for spontaneous symmetry breaking, which are discussed., SCOPUS: ar.j, info:eu-repo/semantics/published

We investigate the properties of a two-dimensional quasicrystal in the presence of a uniform magnetic field. In this configuration, the density of states (DOS) displays a Hofstadter butterfly-like structure when it is represented as a function of the magnetic flux per tile. We show that the low-DOS regions of the energy spectrum are associated with chiral edge states, in direct analogy with the Chern insulators realized with periodic lattices. We establish the topological nature of the edge states by computing the topological Chern number associated with the bulk of the quasicrystal. This topological characterization of the non-periodic lattice is achieved through a local (real-space) topological marker. This work opens a route for the exploration of topological insulating materials in a wide range of non-periodic lattice systems, including photonic crystals and cold atoms in optical lattices., Comment: 10 pages, 9 figures. Published version

A study is reported of the quantum scattering resonances of dissociating molecules using a semiclassical approach based on periodic-orbit theory. The dynamics takes place on a potential energy surface with an energy barrier separating two channels of dissociation. Above the barrier, the unstable symmetric-stretch periodic orbit may undergo a supercritical pitchfork bifurcation, leading to a classically chaotic regime. Signatures of the bifurcation appear in the spectrum of resonances, which have a shorter lifetime than classically expected. A method is proposed to evaluate semiclassically the energy and lifetime of the quantum resonances in this intermediate regime.

An overview is given of recent advances in nonequilibrium statistical mechanics about the statistics of random paths and current fluctuations. Although statistics is carried out in space for equilibrium statistical mechanics, statistics is considered in time or spacetime for nonequilibrium systems. In this approach, relationships have been established between nonequilibrium properties such as the transport coefficients, the thermodynamic entropy production, or the affinities, and quantities characterizing the microscopic Hamiltonian dynamics and the chaos or fluctuations it may generate. This overview presents results for classical systems in the escape-rate formalism, stochastic processes, and open quantum systems.

We present a treatment of many-body Fermionic systems that facilitates an expression of the well-known quantities in a series expansion of the Planck's constant. The ensuing semiclassical result contains to a leading order of the response function the classical time correlation function of the observable followed by the Weyl-Wigner series, on top of these terms are the periodic-orbit correction terms. The treatment given here starts from linear response assumption of the many-body theory and in its connection with semiclassical theory, it makes no assumption of the integrability of classical dynamics underlying the one-body quantal system. Applications of the framework are also discussed., Comment: 18 pages, TeX

Information erasure at the molecular scale during the depolymerization of copolymers is shown to require a minimum entropy production in accordance with Landauer's principle and as a consequence of the second law of thermodynamics. This general result is illustrated with an exactly solvable model of copolymerization, which also shows that the minimum entropy production that is possible for a specific molecular mechanism of depolymerization may be larger than the minimum required by Landauer's principle.

A theoretical study is reported of electron transport at finite temperature in a double quantum dot (DQD) capacitively coupled to a quantum point contact (QPC) for the measurement of the DQD charge state. Starting from a Hamiltonian model, a master equation is obtained for the stochastic process taking place in the DQD while the QPC is at or away from equilibrium, allowing us to study the measurement back-action of the QPC onto the DQD. The QPC is treated nonperturbatively in our analysis. Effective fluctuation theorems are established for the full counting statistics of the DQD current under different limiting conditions. These fluctuation theorems hold with respect to an effective affinity characterizing the nonequilibrium environment of the DQD and differing from the applied voltage if the QPC is out of equilibrium. The effective affinity may even change its sign if the Coulomb drag of the QPC reverses the DQD current. The thermodynamic implications of the effective fluctuation theorems are discussed.

Using path-integral methods, a formula is deduced for the noise-induced escape rate from an attracting fixed point across an unstable fixed point in one-dimensional maps. The calculation starts from the trace formula for the eigenvalues of the Frobenius-Perron operator ruling the time evolution of the probability density in noisy maps. The escape rate is determined from the loop formed by two heteroclinic orbits connecting back and forth the two fixed points of the one-dimensional map extended to a two-dimensional symplectic map. The escape rate is obtained with the expression of the prefactor to Arrhenius-van't Hoff exponential factor.

The chaotic scattering theory is here extended to obtain escape-rate expressions for the transport coefficients appropriate for a simple classical fluid, or for a chemically reacting system. This theory allows various transport coefficients such as the coefficients of viscosity, thermal conductivity, etc., to be expressed in terms of the positive Lyapunov exponents and Kolmogorov-Sinai entropy of a set of phase space trajectories that take place on an appropriate fractal repeller. This work generalizes the previous results of Gaspard and Nicolis for the coefficient of diffusion of a particle moving in a fixed array of scatterers., Comment: 27 pages LaTeX, no figures

A time-reversal symmetry relation is established for out-of-equilibrium dilute or rarefied gases described by the fluctuating Boltzmann equation. The relation is obtained from the associated coarse-grained master equation ruling the random numbers of particles in cells of given position and velocity in the single-particle phase space. The symmetry relation concerns the fluctuating particle and energy currents of the gas flowing between reservoirs or thermalizing surfaces at given particle densities or temperatures., The result of this paper has been presented at the conference "Boltzmann equation: mathematics, modeling and simulations" in memory of Carlo Cercignani at the Henri Poincar\'e Institute, Paris, February 9-11, 2011

The counting statistics of electron transport is theoretically studied in a system with two capacitively coupled parallel transport channels. Each channel is composed of a quantum dot connected by tunneling to two reservoirs. The nonequilibrium steady state of the system is controlled by two affinities or thermodynamic forces, each one determined by the two reservoirs of each channel. The status of a single-current fluctuation theorem is investigated starting from the fundamental two-current fluctuation theorem, which is a consequence of microreversibility. We show that the single-current fluctuation theorem holds in the limit of a large Coulomb repulsion between the two parallel quantum dots, as well as in the limit of a large current ratio between the parallel channels. In this latter limit, the symmetry relation of the single-current fluctuation theorem is satisfied with respect to an effective affinity that is much lower than the affinity determined by the reservoirs. This back-action effect is quantitatively characterized., Comment: 15 pages, 9 figures

Generalizations of Onsager reciprocity relations are established for the nonlinear response coefficients of ballistic transport in the effusion of gaseous mixtures. These generalizations, which have been established on the basis of the fluctuation theorem for the currents, are here considered for mass separation by effusion. In this kinetic process, the mean values of the currents depend nonlinearly on the affinities or thermodynamic forces controlling the nonequilibrium constraints. These nonlinear transport effects are shown to play an important role in the process of mass separation. In particular, the entropy efficiency turns out to be significantly larger than it would be the case if the currents were supposed to depend linearly on the affinities.

We consider the three-dimensional dynamics of systems of many interacting hard spheres, each individually confined to a dispersive environment, and show that the macroscopic limit of such systems is characterized by a coefficient of heat conduction whose value reduces to a dimensional formula in the limit of vanishingly small rate of interaction. It is argued that this limit arises from an effective loss of memory. Similarities with the diffusion of a tagged particle in binary mixtures are emphasized., Comment: Submitted to Chaos, special issue "Statistical Mechanics and Billiard-Type Dynamical Systems"

The effect of noise is studied in one-dimensional maps undergoing transcritical, tangent, and pitchfork bifurcations. The attractors of the noiseless map become metastable states in the presence of noise. In the weak-noise limit, a symplectic two-dimensional map is associated with the original one-dimensional map. The consequences of their noninvertibility on the phase-space structures are discussed. Heteroclinic orbits are identified which play a key role in the determination of the escape rates from the metastable states. Near bifurcations, the critical slowing down justifies the use of a continuous-time approximation replacing maps by flows, which allows the analytic calculation of the escape rates. This method provides the universal scaling behavior of the escape rates at the bifurcations., Comment: 16 pages, 11 figures, submitted to Physical Review E

Galton boards are models of deterministic diffusion in a uniform external field, akin to driven periodic Lorentz gases, here considered in the absence of dissipation mechanism. Assuming a cylindrical geometry with axis along the direction of the external field, the two-dimensional board becomes a model for one-dimensional mass transport along the direction of the external field. This is a purely diffusive process which admits fractal non-equilibrium stationary states under flux boundary conditions. Analytical results are obtained for the statistics of multi-baker maps modeling such a non-uniform diffusion process. A correspondence is established between the local phase-space statistics and their macroscopic counter-parts. The fractality of the invariant state is shown to be responsible for the positiveness of the entropy production rate., Comment: Second of two papers, 17 double column pages, 10 figures

We study the properties of an ultracold Fermi gas loaded in an optical square lattice and subjected to an external and classical non-Abelian gauge field. We show that this system can be exploited as an optical analogue of relativistic quantum electrodynamics, offering a remarkable route to access the exotic properties of massless Dirac fermions with cold atoms experiments. In particular we show that the underlying Minkowski space-time can also be modified, reaching anisotropic regimes where a remarkable anomalous quantum Hall effect and a squeezed Landau vacuum could be observed., 4 pages, 3 figures + additional references

Nowadays it is experimentally feasible to create artificial, and in particular, non-Abelian gauge potentials for ultracold atoms trapped in optical lattices. Motivated by this fact, we investigate the fundamental properties of an ultracold Fermi gas in a non-Abelian U(2) gauge potential characterized by a constant Wilson loop. Under this specific condition, the energy spectrum exhibits a robust band structure with large gaps and reveals a new fractal figure. The transverse conductivity is related to topological invariants and is shown to be quantized when the Fermi energy lies inside a gap of the spectrum. We demonstrate that the analogue of the integer quantum Hall effect for neutral atoms survives the non-Abelian coupling and leads to a striking fractal phase diagram. Moreover, this coupling induces an anomalous Hall effect as observed in graphene., 12 pages, 2 appendices, 7 figures, extended version of arXiv:0712.2571

We study heat transport in a class of stochastic energy exchange systems that characterize the interactions of networks of locally trapped hard spheres under the assumption that neighbouring particles undergo rare binary collisions. Our results provide an extension to three-dimensional dynamics of previous ones applying to the dynamics of confined two-dimensional hard disks [Gaspard P & Gilbert T On the derivation of Fourier's law in stochastic energy exchange systems J Stat Mech (2008) P11021]. It is remarkable that the heat conductivity is here again given by the frequency of energy exchanges. Moreover the expression of the stochastic kernel which specifies the energy exchange dynamics is simpler in this case and therefore allows for faster and more extensive numerical computations., 21 pages, 5 figures

International audience; We present a tight-binding potential for transition metals, carbon, and transition-metal carbides, which has been optimized through a systematic fitting procedure. A minimal basis, including the s and p electrons of carbon and the d electrons of the transition metal, is used to obtain a transferable tight-binding model of the carbon-carbon, metal-metal, and metal-carbon interactions applicable to binary systems. The Ni-C system is more specifically discussed. The successful validation of the potential for different atomic configurations indicates a good transferability of the model and makes it a good choice for atomistic simulations sampling a large configuration space. This approach appears to be very efficient to describe interactions in systems containing carbon and transition-metal elements. By way of example, we present results concerning the epitaxial growth of graphene sheets on (111) Ni surfaces, as well as the catalytic nucleation of carbon nanotubes.

Deterministic diffusive systems such as the periodic Lorentz gas, multi-baker map, as well as spatially periodic systems of interacting particles, have non-equilibrium stationary states with fractal properties when put in contact with particle reservoirs at their boundaries. We study the macroscopic limits of these systems and establish a correspondence between the thermodynamics of the macroscopic diffusion process and the fractality of the stationary states that characterize the phase-space statistics. In particular the entropy production rate is recovered from first principles using a formalism due to Gaspard [J. Stat. Phys. 88, 1215 (1997)]. This article is the first of two; the second article considers the influence of a uniform external field on such systems., Comment: First of two papers. 14 double column pages, 7 figures

We present a first-principles study of heat conduction in a class of models which exhibit a new multi-step local thermalization mechanism which gives rise to Fourier's law. Local thermalization in our models occurs as the result of binary collisions among locally confined gas particles. We explore the conditions under which relaxation to local equilibrium, which involves no energy exchange, takes place on time scales shorter than that of the binary collisions which induce local thermalization. The role of this mechanism in multi-phase material systems such as aerogels is discussed., 4 pages, 3 color figures, to appear in Physical Review Letters

A universal quantum work relation is proved for isolated time-dependent Hamiltonian systems in a magnetic field as the consequence of microreversibility. This relation involves a functional of an arbitrary observable. The quantum Jarzynski equality is recovered in the case this observable vanishes. The Green-Kubo formula and the Casimir-Onsager reciprocity relations are deduced thereof in the linear response regime.