Ensemble Dependence of the Transient Fluctuation Theorem

The Fluctuation Theorem gives an analytical expression for the probability of observing second law violating dynamical fluctuations, in nonequilibrium systems. At equilibrium statistical mechanical fluctuations are known to be ensemble dependent. In this paper we generalise the Transient and Steady State Fluctuation Theorems to various nonequilibrium dynamical ensembles. The Transient and Steady State Fluctuation Theorem for an isokinetic ensemble of isokinetic trajectories is tested using nonequilibrium molecular dynamics simulations of shear flow.Comment: 16 pages, 1 table, 4 figures; presentation of generalised formulae and discussion clarifie

Ensemble Dependence of the Transient Fluctuation Theorem

The Fluctuation Theorem gives an analytical expression for the probability of observing second law violating dynamical fluctuations, in nonequilibrium systems. At equilibrium statistical mechanical fluctuations are known to be ensemble dependent. In this paper we generalise the Transient and Steady State Fluctuation Theorems to various nonequilibrium dynamical ensembles. The Transient and Steady State Fluctuation Theorem for an isokinetic ensemble of isokinetic trajectories is tested using nonequilibrium molecular dynamics simulations of shear flow.We would like to thank the Australian Research Council for the support of this project

The Fluctuation Theorem and Green-Kubo Relations

Green-Kubo and Einstein expressions for the transport coefficients of a fluid in a nonequilibrium steady state can be derived using the Fluctuation Theorem and by assuming the probability distribution of the time-averaged dissipative flux is Gaussian. These expressions are consistent with those obtained using linear response theory and are valid in the linear regime. It is shown that these expressions are however, not valid in the nonlinear regime where the fluid is driven far from equilibrium. We advance an argument for why these expression are only valid in the linear response, zero field limit.Comment: 32 pages, inc. 6 figures Discussion and notation improve

Statistical Mechanics of Time Independent Non-Dissipative Nonequilibrium States

We examine the question of whether the formal expressions of equilibrium statistical mechanics can be applied to time independent non-dissipative systems that are not in true thermodynamic equilibrium and are nonergodic. By assuming the phase space may be divided into time independent, locally ergodic domains, we argue that within such domains the relative probabilities of microstates are given by the standard Boltzmann weights. In contrast to previous energy landscape treatments, that have been developed specifically for the glass transition, we do not impose an a priori knowledge of the inter-domain population distribution. Assuming that these domains are robust with respect to small changes in thermodynamic state variables we derive a variety of fluctuation formulae for these systems. We verify our theoretical results using molecular dynamics simulations on a model glass forming system. Non-equilibrium Transient Fluctuation Relations are derived for the fluctuations resulting from a sudden finite change to the system's temperature or pressure and these are shown to be consistent with the simulation results. The necessary and sufficient conditions for these relations to be valid are that the domains are internally populated by Boltzmann statistics and that the domains are robust. The Transient Fluctuation Relations thus provide an independent quantitative justification for the assumptions used in our statistical mechanical treatment of these systems.Comment: 17 pages, 4 figures, minor amendment

New observations regarding deterministic, time reversible thermostats and Gauss's principle of least constraint

Deterministic thermostats are frequently employed in non-equilibrium molecular dynamics simulations in order to remove the heat produced irreversibly over the course of such simulations. The simplest thermostat is the Gaussian thermostat, which satisfies Gauss's principle of least constraint and fixes the peculiar kinetic energy. There are of course infinitely many ways to thermostat systems, e.g. by fixing $\sum\limits_i{|{p_i}|^{\mu + 1}}$. In the present paper we provide, for the first time, convincing arguments as to why the conventional Gaussian isokinetic thermostat ($\mu=1$) is unique in this class. We show that this thermostat minimizes the phase space compression and is the only thermostat for which the conjugate pairing rule (CPR) holds. Moreover it is shown that for finite sized systems in the absence of an applied dissipative field, all other thermostats ($\mu=1$) perform work on the system in the same manner as a dissipative field while simultaneously removing the dissipative heat so generated. All other thermostats ($\mu=1$) are thus auto-dissipative. Among all $\mu$-thermostats, only the $\mu=1$ Gaussian thermostat permits an equilibrium state.Comment: 27 pages including 10 figures; submitted for publication Journal of Chemical Physic

The rheology of solid glass

As the glass transition is approached from the high temperature side, viewed as a liquid, the properties of the ever more viscous supercooled liquid are continuous functions of temperature and pressure. The point at which we decide to classify the fluid as a solid is therefore subjective. This subjective decision does, however, have discontinuous consequences for how we determine the rheological properties of the glass. We apply the recently discovered relaxation theorem to the time independent, nondissipative, nonergodic glassy state to derive an expression for the phase space distribution of an ensemble of glass samples. This distribution is then used to construct a time dependent linear response theory for aged glassysolids. The theory is verified using molecular dynamics simulations of oscillatory shear for a realistic model glass former with excellent agreement being obtained between the response theory calculations and direct nonequilibrium molecular dynamics calculations. Our numerical results confirm that unlike all the fluid states, including supercooled liquids, a solidglass (in common with crystalline states) has a nonzero value for the zero frequency shear modulus. Of all the states of matter, a supercooled fluid approaching the glass transition has the highest value for the limiting zero frequency shear viscosity. Finally, solidglasses like dilute gases and crystals have a positive temperature coefficient for the shear viscosity whereas supercooled and normal liquids have a negative temperature coefficient.We thank the National Computational Infrastructure NCI for computational facilities and the Australian Research Council ARC for funding

On the Application of the Gallavotti-Cohen Fluctuation Relation to Thermostatted Steady States Near Equilibrium

The fluctuation relation of the Gallavotti-Cohen Fluctuation Theorem (GCFT) concerns fluctuations in the phase space compression rate of dissipative, reversible dynamical systems. It has been proven for Anosov systems, but it is expected to apply more generally. This raises the question of which non-Anosov systems satisfy the fluctuation relation. We analyze time dependent fluctuations in the phase space compression rate of a class of N-particle systems that are at equilibrium or in near equilibrium steady states. This class does not include Anosov systems or isoenergetic systems, however, it includes most steady state systems considered in molecular dynamics simulations of realistic systems. We argue that the fluctuations of the phase space compression rate of these systems at or near equilibrium do not satisfy the fluctuation relation of the GCFT, although the discrepancies become somewhat smaller as the systems move further from equilibrium. In contrast, similar fluctuation relations for an appropriately defined dissipation function appear to hold both near and far from equilibrium.Comment: 46 pages, for publication in PR

Generalised Fluctuation Formula

We develop a General Fluctuation Formula for phase variables that are odd under time reversal. Simulations are used to verify the new formula.Comment: 10 pages, 5 figures, submitted to Procedings of the 3rd Tohwa University International Conference of Statistical Physics, Nov 8-12, 1999 (AIP Conferences Series