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

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

Verification of time-reversibility requirementfor systems satisfying the Evans-Searles fluctuation theorem

The Evans-Searles fluctuation theorem (ESFT) has been shown to be applicable in the near- and far-from-equilibrium regimes for systems with both constant and time-dependent external fields. The derivations of the ESFT have assumed that the external field has a definite parity under a time-reversal mapping. In the present paper, we confirm that the time-reversibility of the system dynamics is a necessary condition for the ESFT to hold. The manner in which the ESFT fails for systems that are not time-reversible is presented, and results are shown which demonstrate that systems which fail to satisfy the ESFT may still satisfy the Crooks relation (CR)

On the relaxation to nonequilibrium steady states

The issue of relaxation has been addressed in terms of ergodic theory in the past. However, the application of that theory to models of physical interest is problematic, especially when dealing with relaxation to nonequilibrium steady states. Here, we consider the relaxation of classical, thermostatted particle systems to equilibrium as well as to nonequilibrium steady states, using dynamical notions including decay of correlations. We show that the condition known as {\Omega}T-mixing is necessary and sufficient to prove relaxation of ensemble averages to steady state values. We then observe that the condition known as weak T-mixing applied to smooth observables is sufficient for relaxation to be independent of the initial ensemble. Lastly, weak T-mixing for integrable functions makes relaxation independent of the ensemble member, apart from a negligible set of members enabling the result to be applied to observations from a single physical experiment. The results also allow us to give a microscopic derivation of Prigogine's principle of minimum entropy production in the linear response regime. The key to deriving these results lies in shifting the discussion from characteristics of dynamical systems, such as those related to metric transitivity, to physical measurements and to the behaviour of observables. This naturally leads to the notion of physical ergodicity.Comment: 44 pages, 1 figur

Optical Spectroscopy of Massive Binary Stars

This is a spectroscopic and photometric study of suspected close binary systems among the massive stars. The stars studied here include stars with temperatures ranging from 45,000 Kelvin (K) to 15,000 K, corresponding to spectral types ranging from O3 V to B5 III, masses between 47 Solar Masses and 5 Solar Masses, and absolute V magnitudes from -6.28 to -2.0. I categorize 30 targets according to my spectroscopic observations into groups with no radial velocity variability, single-lined, and double-lined variability. My analysis of the 18 constant velocity stars results in estimates of stellar effective temperature, Teff, gravity, log g, projected rotational velocity, v sin i, and spectral classification. Analyzing single-lined systems, I find the same stellar parameters for five more systems, and also present the first orbits for these systems. I also explore the probable characteristics of the unseen companions in these systems. Three double-lined systems, two eclipsing and one with an ellipsoidal variation in the light curve, are fully analyzed, and I present important astrophysical parameters for each of these systems, including stellar masses, radii, ages, and distances to each system. The masses are accurate to 4.3% and 3.6% for the primary and secondary for LH 54-425, 2.1% and 1.6% for HI Mon, and 1.1% and 0.6% for HD 42401. Two more double-lined systems are studied, and preliminary results are presented. Photometric observations are analyzed for 56 targets from the All Sky Automated Survey in order to facilitate spectroscopic observations at key points in the binary orbit where spectral features of both components will be well separated. New spectroscopic observations of these eclipsing binaries with my computed ephemerides will allow us to obtain double-lined orbital elements and determine their masses, radii, ages, and distances. These computed parameters will then allow for comparison with theoretical stellar models, and a better understanding of the evolution of massive stars

The Glass Transition and the Jarzynski Equality

A simple model featuring a double well potential is used to represent a liquid that is quenched from an ergodic state into a history dependent glassy state. Issues surrounding the application of the Jarzynski Equality to glass formation are investigated. We demonstrate that the Jarzynski Equality gives the free energy difference between the initial state and the state we would obtain if the glass relaxed to true thermodynamic equilibrium. We derive new variations of the Jarzynski Equality which are relevant to the history dependent glassy state rather than the underlying equilibrium state. It is shown how to compute the free energy differences for the nonequilibrium history dependent glassy state such that it remains consistent with the standard expression for the entropy and with the second law inequality.Comment: 16 pages, 5 figure

Fluctuation Theorems

Fluctuation theorems, which have been developed over the past 15 years, have resulted in fundamental breakthroughs in our understanding of how irreversibility emerges from reversible dynamics, and have provided new statistical mechanical relationships for free energy changes. They describe the statistical fluctuations in time-averaged properties of many-particle systems such as fluids driven to nonequilibrium states, and provide some of the very few analytical expressions that describe nonequilibrium states. Quantitative predictions on fluctuations in small systems that are monitored over short periods can also be made, and therefore the fluctuation theorems allow thermodynamic concepts to be extended to apply to finite systems. For this reason, fluctuation theorems are anticipated to play an important role in the design of nanotechnological devices and in understanding biological processes. These theorems, their physical significance and results for experimental and model systems are discussed.Comment: A review, submitted to Annual Reviews in Physical Chemistry, July 2007 Acknowledgements corrected in revisio

Linearized large signal modeling, analysis, and control design of phase-controlled series-parallel resonant converters using state feedback

This paper proposes a linearized large signal state-space model for the fixed-frequency phase-controlled series-parallel resonant converter. The proposed model utilizes state feedback of the output filter inductor current to perform linearization. The model combines multiple-frequency and average state-space modeling techniques to generate an aggregate model with dc state variables that are relatively easier to control and slower than the fast resonant tank dynamics. The main objective of the linearized model is to provide a linear representation of the converter behavior under large signal variation which is suitable for faster simulation and large signal estimation/calculation of the converter state variables. The model also provides insight into converter dynamics as well as a simplified reduced order transfer function for PI closed-loop design. Experimental and simulation results from a detailed switched converter model are compared with the proposed state-space model output to verify its accuracy and robustness