Reply to "Comment on 'Validity of path thermodynamic description of reactive systems: Microscopic simulations' ".

The Comment's author argues that a correct description of reactive systems should incorporate an explicit interaction with reservoirs, leading to a unified system-reservoir entity. However, this proposition has two major flaws. First, as we will emphasize, this entity inherently follows a thermodynamic equilibrium distribution. In the Comment, no indication is provided on how to maintain such a system-reservoir entity in a nonequilibrium state. Second, contrary to the author's claim, the inclusion of a system-reservoir interaction in the traditional stochastic modeling of reactive systems does not automatically alter the limited applicability of path thermodynamics to problematic reactive systems. We will provide a simple demonstration to illustrate that certain elementary reactions may not involve any changes in reservoir components, which seem to have been overlooked by the author.

Validity of path thermodynamic description of reactive systems: Microscopic simulations.

Traditional stochastic modeling of reactive systems limits the domain of applicability of the associated path thermodynamics to systems involving a single elementary reaction at the origin of each observed change in composition. An alternative stochastic modeling has recently been proposed to overcome this limitation. These two ways of modeling reactive systems are in principle incompatible. The question thus arises about choosing the appropriate type of modeling to be used in practical situations. In the absence of sufficiently accurate experimental results, one way to address this issue is through the microscopic simulation of reactive fluids, usually based on hard-sphere dynamics in the Boltzmann limit. In this paper, we show that results obtained through such simulations unambiguously confirm the predictions of traditional stochastic modeling, invalidating a recently proposed alternative.

Fluctuation theorem: A critical review.

Fluctuation theorem for entropy production is revisited in the framework of stochastic processes. The applicability of the fluctuation theorem to physico-chemical systems and the resulting stochastic thermodynamics were analyzed. Some unexpected limitations are highlighted in the context of jump Markov processes. We have shown that these limitations handicap the ability of the resulting stochastic thermodynamics to correctly describe the state of non-equilibrium systems in terms of the thermodynamic properties of individual processes therein. Finally, we considered the case of diffusion processes and proved that the fluctuation theorem for entropy production becomes irrelevant at the stationary state in the case of one variable systems.

Nonlinear analysis of the shearing instability in granular gases

It is known that a finite-size homogeneous granular fluid develops a hydrodynamiclike instability when dissipation crosses a threshold value. This instability is analyzed in terms of modified hydrodynamic equations: first, a source term is added to the energy equation which accounts for the energy dissipation at collisions and the phenomenological Fourier law is generalized according to previous results. Second, a rescaled time formalism is introduced that maps the homogeneous cooling state into a nonequilibrium steady state. A nonlinear stability analysis of the resulting equations is done which predicts the appearance of flow patterns. A stable modulation of density and temperature is produced that does not lead to clustering. Also a global decrease of the temperature is obtained, giving rise to a decrease of the collision frequency and dissipation rate. Good agreement with molecular dynamics simulations of inelastic hard disks is found for low dissipation.