Quantum work relations and response theory

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

Microscopic reversibility of quantum open systems

The transition probability for time-dependent unitary evolution is invariant under the reversal of protocols just as in the classical Liouvillian dynamics. In this article, we generalize the expression of microscopic reversibility to externally perturbed large quantum open systems. The time-dependent external perturbation acts on the subsystem during a transient duration, and subsequently the perturbation is switched off so that the total system would thermalize. We concern with the transition probability for the subsystem between the initial and final eigenstates of the subsystem. In the course of time evolution, the energy is irreversibly exchanged between the subsystem and reservoir. The time reversed probability is given by the reversal of the protocol and the initial ensemble. Microscopic reversibility equates the time forward and reversed probabilities, and therefore appears as a thermodynamic symmetry for open quantum systems.Comment: numerical demonstration is correcte

Fluctuation theorem for currents in open quantum systems

A quantum-mechanical framework is set up to describe the full counting statistics of particles flowing between reservoirs in an open system under time-dependent driving. A symmetry relation is obtained which is the consequence of microreversibility for the probability of the nonequilibrium work and the transfer of particles and energy between the reservoirs. In some appropriate long-time limit, the symmetry relation leads to a steady-state quantum fluctuation theorem for the currents between the reservoirs. On this basis, relationships are deduced which extend the Onsager-Casimir reciprocity relations to the nonlinear response coefficients.Comment: 19 page

Stochastic thermodynamics of chemical reaction networks

For chemical reaction networks described by a master equation, we define energy and entropy on a stochastic trajectory and develop a consistent nonequilibrium thermodynamic description along a single stochastic trajectory of reaction events. A first-law like energy balance relates internal energy, applied (chemical) work and dissipated heat for every single reaction. Entropy production along a single trajectory involves a sum over changes in the entropy of the network itself and the entropy of the medium. The latter is given by the exchanged heat identified through the first law. Total entropy production is constrained by an integral fluctuation theorem for networks arbitrarily driven by time-dependent rates and a detailed fluctuation theorem for networks in the steady state. Further exact relations like a generalized Jarzynski relation and a generalized Clausius inequality are discussed. We illustrate these results for a three-species cyclic reaction network which exhibits nonequilibrium steady states as well as transitions between different steady states.Comment: 14 pages, 2 figures, accepted for publication in J. Chem. Phy

Gallavotti-Cohen-Type symmetry related to cycle decompositions for Markov chains and biochemical applications

We slightly extend the fluctuation theorem obtained in \cite{LS} for sums of generators, considering continuous-time Markov chains on a finite state space whose underlying graph has multiple edges and no loop. This extended frame is suited when analyzing chemical systems. As simple corollary we derive in a different method the fluctuation theorem of D. Andrieux and P. Gaspard for the fluxes along the chords associated to a fundamental set of oriented cycles \cite{AG2}. We associate to each random trajectory an oriented cycle on the graph and we decompose it in terms of a basis of oriented cycles. We prove a fluctuation theorem for the coefficients in this decomposition. The resulting fluctuation theorem involves the cycle affinities, which in many real systems correspond to the macroscopic forces. In addition, the above decomposition is useful when analyzing the large deviations of additive functionals of the Markov chain. As example of application, in a very general context we derive a fluctuation relation for the mechanical and chemical currents of a molecular motor moving along a periodic filament.Comment: 23 pages, 5 figures. Correction

Modified Fluctuation-dissipation theorem for non-equilibrium steady-states and applications to molecular motors

We present a theoretical framework to understand a modified fluctuation-dissipation theorem valid for systems close to non-equilibrium steady-states and obeying markovian dynamics. We discuss the interpretation of this result in terms of trajectory entropy excess. The framework is illustrated on a simple pedagogical example of a molecular motor. We also derive in this context generalized Green-Kubo relations similar to the ones derived recently by Seifert., Phys. Rev. Lett., 104, 138101 (2010) for more general networks of biomolecular states.Comment: 6 pages, 2 figures, submitted in EP

Fluctuation theorem for the effusion of an ideal gas

The probability distribution of the entropy production for the effusion of an ideal gas between two compartments is calculated explicitly. The fluctuation theorem is verified. The analytic results are in good agreement with numerical data from hard disk molecular dynamics simulations.Comment: 11 pages, 10 figures, 2 table

Thermodynamic large fluctuations from uniformized dynamics

Large fluctuations have received considerable attention as they encode information on the fine-scale dynamics. Large deviation relations known as fluctuation theorems also capture crucial nonequilibrium thermodynamical properties. Here we report that, using the technique of uniformization, the thermodynamic large deviation functions of continuous-time Markov processes can be obtained from Markov chains evolving in discrete time. This formulation offers new theoretical and numerical approaches to explore large deviation properties. In particular, the time evolution of autonomous and non-autonomous processes can be expressed in terms of a single Poisson rate. In this way the uniformization procedure leads to a simple and efficient way to simulate stochastic trajectories that reproduce the exact fluxes statistics. We illustrate the formalism for the current fluctuations in a stochastic pump model

Fluctuation theorem for currents and Schnakenberg network theory

A fluctuation theorem is proved for the macroscopic currents of a system in a nonequilibrium steady state, by using Schnakenberg network theory. The theorem can be applied, in particular, in reaction systems where the affinities or thermodynamic forces are defined globally in terms of the cycles of the graph associated with the stochastic process describing the time evolution.Comment: new version : 16 pages, 1 figure, to be published in Journal of Statistical Physic