arXiv subjects

Pierre Gaspard

Publications and source records attributed to Pierre Gaspard.

At least 55 records · Page 3Linked to original sources

arXiv2018

Microreversibility, nonequilibrium current fluctuations, and response theory

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.

cond-mat.stat-mech↗

arXiv2018

Stochastic approach and fluctuation theorem for charge transport in diodes

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.

cond-mat.stat-mech↗

arXiv2018

Nonequilibrium thermodynamics and boundary conditions for reaction and transport in heterogeneous media

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 is 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.

physics.chem-ph↗

arXiv2018

Reaction kinetics in open reactors and serial transfers between closed reactors

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.

cond-mat.stat-mech↗

arXiv2018

Dynamics of Janus motors with microscopically reversible kinetics

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 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.

cond-mat.soft↗

arXiv2018

Fluctuating chemohydrodynamics and the stochastic motion of self-diffusiophoretic particles

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.

cond-mat.stat-mech↗

arXiv2017

Mechanochemical fluctuation theorem and thermodynamics of self-phoretic motors

Microscopic dynamical aspects of the propulsion of nanomotors by self-phoretic mechanisms are considered. Propulsion by self-diffusiophoresis relies on the mechanochemical coupling between the fluid velocity field and the concentration fields induced by asymmetric catalytic reactions on the motor surface. The consistency between the thermodynamics of this coupling and the microscopic reversibility of the underlying molecular dynamics is investigated. For this purpose coupled Langevin equations for the translational, rotational, and chemical fluctuations of self-phoretic motors are derived. A mechanochemical fluctuation theorem for the joint probability to find the motor at position r after n reactive events have occurred during the time interval t is also derived. An important result that follows from this analysis is the identification of an effect that is reciprocal to self-propulsion by diffusiophoresis, which leads to the possibility of fuel synthesis by mechanochemical coupling to external force and torque.

cond-mat.stat-mech↗

arXiv2017

Dynamical contribution to the heat conductivity in stochastic energy exchanges of locally confined gases

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.

cond-mat.stat-mech↗

arXiv2016

Growth and dissolution of macromolecular Markov chains

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.

physics.chem-ph↗

arXiv2016

Kinetics and thermodynamics of exonuclease-deficient DNA polymerases

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.

q-bio.SC↗

arXiv2016

Kinetics and thermodynamics of DNA polymerases with exonuclease proofreading

Kinetic theory and thermodynamics are applied to DNA polymerases with exonuclease activity, taking into account the dependence of the rates on the previously incorportated nucleotide. The replication fidelity is shown to increase significantly thanks to this dependence at the basis of the mechanism of exonuclease proofreading. In particular, this dependence can provide up to a hundred-fold lowering of the error probability under physiological conditions. Theory is compared with numerical simulations for the DNA polymerases of T7 viruses and human mitochondria.

q-bio.SC↗

arXiv2015

Fluctuation relations for equilibrium states with broken discrete or continuous symmetries

Isometric fluctuation relations are deduced for the fluctuations of the order parameter in equilibrium systems of condensed-matter physics with broken discrete or continuous symmetries. These relations are similar to their analogues obtained for non-equilibrium systems where the broken symmetry is time reversal. At equilibrium, these relations show that the ratio of the probabilities of opposite fluctuations goes exponentially with the symmetry-breaking external field and the magnitude of the fluctuations. These relations are applied to the Curie-Weiss, Heisenberg, and $XY$~models of magnetism where the continuous rotational symmetry is broken, as well as to the $q$-state Potts model and the $p$-state clock model where discrete symmetries are broken. Broken symmetries are also considered in the anisotropic Curie-Weiss model. For infinite systems, the results are calculated using large-deviation theory. The relations are also applied to mean-field models of nematic liquid crystals where the order parameter is tensorial. Moreover, their extension to quantum systems is also deduced.

cond-mat.stat-mech↗

arXiv2015

Topological Hofstadter Insulators in a Two-Dimensional Quasicrystal

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.

cond-mat.mes-hall↗

arXiv2014

Signatures of classical bifurcations in the quantum scattering resonances of dissociating molecules

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.

physics.chem-ph↗

arXiv2014

Random paths and current fluctuations in nonequilibrium statistical mechanics

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.

cond-mat.stat-mech↗

arXiv2013

Information erasure in copolymers

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.

cond-mat.stat-mech↗

arXiv2013

Effective fluctuation theorems for electron transport in a double quantum dot coupled to a quantum point contact

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). 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 backaction of the QPC onto the DQD. The QPC is treated non-perturbatively 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.

cond-mat.mes-hall↗

arXiv2012

Dynamical Aspects of Information in Copolymerization Processes

Natural supports of information are given by random copolymers such as DNA or RNA where information is coded in the sequence of covalent bonds. At the molecular scale, the stochastic growth of a single copolymer with or without a template proceeds by successive random attachments or detachments of monomers continuously supplied by the surrounding solution. The thermodynamics of copolymerization shows that fundamental links already exist between information and thermodynamics at the molecular scale, which opens new perspectives to understand the dynamical aspects of information in biology.

q-bio.BM↗