Search Results (41)

In the present work, we suggest a new approach for studying the equilibrium states of an hydrodynamic isothermal turbulent self-gravitating system as a statistical model for a molecular cloud. The main hypothesis is that the local turbulent motion of the fluid elements is purely chaotic and can be regarded as a perfect gas. Then, the turbulent kinetic energy per fluid element can be substituted for the temperature of the chaotic motion of the fluid elements. Using this, we write down effective formulae for the internal and total the energy and for the first principal of thermodynamics. Then, we obtain expressions for the entropy, the free energy, and the Gibbs potential. Searching for equilibrium states, we explore two possible systems: the canonical ensemble and the grand canonical ensemble. Studying the former, we conclude that there is no extrema for the free energy. Through the latter system, we obtain a minimum of the Gibbs potential when the macro-temperature and pressure of the cloud are equal to those of the surrounding medium. This minimum corresponds to a possible stable local equilibrium state of our system. Full article

We survey developments in the use of entropy maximization for applying the Gibbs Canonical Ensemble to finite situations. Biological insights are invoked along with physical considerations. In the game-theoretic approach to entropy maximization, the interpretation of the two player roles as predator and prey provides a well-justified and symmetric analysis. The main focus is placed on the Lagrange multiplier approach. Using natural physical units with Planck’s constant set to unity, it is recognized that energy has the dimensions of inverse time. Thus, the conjugate Lagrange multiplier, traditionally related to absolute temperature, is now taken with time units and oriented to follow the Arrow of Time. In quantum optics, where energy levels are bounded above and below, artificial singularities involving negative temperatures are eliminated. In a biological model where species compete in an environment with a fixed carrying capacity, use of the Canonical Ensemble solves an instance of Eigen’s phenomenological rate equations. The Lagrange multiplier emerges as a statistical measure of the ecological age. Adding a weak inequality on an order parameter for the entropy maximization, the phase transition from initial unconstrained growth to constrained growth at the carrying capacity is described, without recourse to a thermodynamic limit for the finite system. Full article

This paper concerns interactive Monte Carlo simulations for adiabatic ensembles and a genetic algorithm to research and educational contexts. In the Introduction, we discuss some concepts of thermodynamics, statistical mechanics and ensembles relevant to molecular simulations. The second and third sections of the paper comprise two programs in JavaScript regarding (i) argon in the grand-isobaric ensemble focusing on the direct calculation of entropy, vapor–liquid equilibria and radial distribution functions and (ii) an ideal system of quantized harmonic oscillators in the microcanonical ensemble for the determination of the entropy and Boltzmann distribution, also including the definition of Boltzmann and Gibbs entropies relative to classical systems. The fourth section is concerned with a genetic algorithm program in Java, as a pedagogical alternative to introduce the Second Law of Thermodynamics, which summarizes artificial intelligence methods and the cumulative selection process in biogenesis. Full article

Statistical counting ad infinitum is the holographic observable to a statistical dynamics with finite states under independent and identically distributed N sampling. Entropy provides the infinitesimal probability for an observed empirical frequency $\widehat{\mathit{\nu }}$ with respect to a probability prior $\mathbf{p}$, when $\widehat{\mathit{\nu }}\ne \mathbf{p}$ as $N\to \infty$. Following Callen’s postulate and through Legendre–Fenchel transform, without help from mechanics, we show that an internal energy $\mathbf{u}$ emerges; it provides a linear representation of real-valued observables with full or partial information. Gibbs’ fundamental thermodynamic relation and theory of ensembles follow mathematically. $\mathbf{u}$ is to $\widehat{\mathit{\nu }}$ what chemical potential $\mu$ is to particle number N in Gibbs’ chemical thermodynamics, what $\beta =T^{-1}$ is to internal energy U in classical thermodynamics, and what $\omega$ is to t in Fourier analysis. Full article

Systems with a multistable energy landscape are widespread in physics, biophysics, technology, and materials science. They are strongly influenced by thermal fluctuations and external mechanical actions that can be applied at different rates, moving the system from equilibrium to non-equilibrium regimes. In this paper, we focus on a simple system involving a single breaking phenomenon to describe the various theoretical approaches used to study these problems. To begin with, we propose the exact solution at thermodynamic equilibrium based on the calculation of the partition function without approximations. We then introduce the technique of spin variables, which is able to simplify the treatment even for systems with a large number of coordinates. We then analyze the energy balance of the system to better understand its underlying physics. Finally, we introduce a technique based on transition state theory useful for studying the non-equilibrium dynamical regimes of these systems. This method is appropriate for the evaluation of rate effects and hysteresis loops. These approaches are developed for both the Helmholtz ensemble (prescribed extension) and the Gibbs ensemble (applied force) of statistical mechanics. The symmetry and duality of these two ensembles is discussed in depth. While these techniques are used here for a simple system with theoretical purposes, they can be applied to complex systems of interest for several physical, biophysical, and technological applications. Full article

The quantum statistical properties of the proton subsystem in hydrogen-bonded crystals (HBC) are investigated. Based on the non-stationary Liouville operator equation (taking into account a number of assumptions established in the experiment), a quantum kinetic equation is constructed for the ensemble of non-interacting protons (an ideal proton gas) moving in the crystal potential image perturbed by the external electric field. The balanced density matrix for the unperturbed proton subsystem is constructed using the quantum canonical Gibbs distribution, and the non-balanced density matrix is calculated from the solutions of the nonlinear quantum kinetic equation by methods in linear approximation of perturbation theory for the blocking electrode model. Full quantum mechanical averaging of the polarization operator makes it possible to study the theoretical frequency-temperature spectra of the complex dielectric permittivity (CDP) calculated using quantum relaxation parameters that differ significantly from their semiclassical counterparts. A scheme is presented for an analytical study of the dielectric loss tangent in the region of quantum nonlinear relaxation in HBC. The results obtained in the given paper are of scientific interest in developing the theoretical foundations of proton conduction processes in energy-independent memory elements (with anomalously high residual polarization) based on thin films of ferroelectric materials in the ultralow temperature range (1–10 K). The theoretical results obtained have a direct application to the study of the tunneling mechanisms of spontaneous polarization in ferroelectric HBC with a rectangular hysteresis loop, in particular in crystals of potassium dideutrophosphate (KDP), widely used in nonlinear optics and laser technology. The quantum properties of proton relaxation in HBC can be applied in the future to the study of solid-state electrolytes with high proton conductivity for hydrogen energy, capacitor technology (superionics, varicodes), and elements of MIS and MSM structures in the development of resonant tunnel diodes for microelectronics and computer technology. Full article

We consider an N fermion system at low temperature T in which we encounter special particle number values $N_m$ exhibiting special traits. These values arise when focusing attention upon the degree of mixture (DM) of the pertinent quantum states. Given the coupling constant of the Hamiltonian, the DMs stay constant for all N-values but experience sudden jumps at the $N_m$. For a quantum state described by the matrix $\rho$, its purity is expressed by $Tr{\rho }^2$ and then the degree of mixture is given by $1-Tr{\rho }^2$, a quantity that coincides with the entropy $S_q$ for $q=2$. Thus, Tsallis entropy of index two faithfully represents the degree of mixing of a state, that is, it measures the extent to which the state departs from maximal purity. Macroscopic manifestations of the degree of mixing can be observed through various physical quantities. Our present study is closely related to properties of many-fermion systems that are usually manipulated at zero temperature. Here, we wish to study the subject at finite temperature. The Gibbs ensemble is appealed to. Some interesting insights are thereby gained. Full article

This work scrutinizes, using statistical mechanics indicators, important traits displayed by quantum many-body systems. Our statistical mechanics quantifiers are employed, in the context of Gibbs’ canonical ensemble at temperature T. A new quantifier of this sort is also presented here. The present discussion focuses attention on the role played by the fermion number N in many-fermion dynamics, that is, N is our protagonist. We have discovered discovers particular values of N for which the thermal indicators exhibit unexpected abrupt variations. Such a fact reflects an unanticipated characteristic of fermionic dynamics. Full article

Quite often polymers exhibit different elastic behavior depending on the statistical ensemble (Gibbs vs. Helmholtz). This is an effect of strong fluctuations. In particular, two-state polymers, which locally or globally fluctuate between two classes of microstates, can exhibit strong ensemble inequivalence with negative elastic moduli (extensibility or compressibility) in the Helmholtz ensemble. Two-state polymers consisting of flexible beads and springs have been studied extensively. Recently, similar behavior was predicted in a strongly stretched wormlike chain consisting of a sequence of reversible blocks, fluctuating between two values of the bending stiffness (the so called reversible wormlike chain, rWLC). In this article, we theoretically analyse the elasticity of a grafted rod-like semiflexible filament which fluctuates between two states of bending stiffness. We consider the response to a point force at the fluctuating tip in both the Gibbs and the Helmholtz ensemble. We also calculate the entropic force exerted by the filament on a confining wall. This is done in the Helmholtz ensemble and, under certain conditions, it yields negative compressibility. We consider a two-state homopolymer and a two-block copolymer with two-state blocks. Possible physical realizations of such a system would be grafted DNA or carbon nanorods undergoing hybridization, or grafted F-actin bundles undergoing collective reversible unbinding. Full article

Non-standard thermostatistical formalisms derived from generalizations of the Boltzmann–Gibbs entropy have attracted considerable attention recently. Among the various proposals, the one that has been most intensively studied, and most successfully applied to concrete problems in physics and other areas, is the one associated with the $S_q$ non-additive entropies. The $S_q$-based thermostatistics exhibits a number of peculiar features that distinguish it from other generalizations of the Boltzmann–Gibbs theory. In particular, there is a close connection between the $S_q$-canonical distributions and the micro-canonical ensemble. The connection, first pointed out in 1994, has been subsequently explored by several researchers, who elaborated this facet of the $S_q$-thermo-statistics in a number of interesting directions. In the present work, we provide a brief review of some highlights within this line of inquiry, focusing on micro-canonical scenarios leading to $S_q$-canonical distributions. We consider works on the micro-canonical ensemble, including historical ones, where the $S_q$-canonical distributions, although present, were not identified as such, and also more resent works by researchers who explicitly investigated the $S_q$-micro-canonical connection. Full article

In a wavefunction-only philosophy, thermodynamics must be recast in terms of an ensemble of wavefunctions. In this perspective we study how to construct Gibbs ensembles for magnetic quantum spin models. We show that with free boundary conditions and distinguishable “spins” there are no finite-temperature phase transitions because of high dimensionality of the phase space. Then we focus on the simplest case, namely the mean-field (Curie–Weiss) model, in order to discover whether phase transitions are even possible in this model class. This strategy at least diminishes the dimensionality of the problem. We found that, even assuming exchange symmetry in the wavefunctions, no finite-temperature phase transitions appear when the Hamiltonian is given by the usual energy expression of quantum mechanics (in this case the analytical argument is not totally satisfactory and we relied partly on a computer analysis). However, a variant model with additional “wavefunction energy” does have a phase transition to a magnetized state. (With respect to dynamics, which we do not consider here, wavefunction energy induces a non-linearity which nevertheless preserves norm and energy. This non-linearity becomes significant only at the macroscopic level.) The three results together suggest that magnetization in large wavefunction spin chains appears if and only if we consider indistinguishable particles and block macroscopic dispersion (i.e., macroscopic superpositions) by energy conservation. Our principle technique involves transforming the problem to one in probability theory, then applying results from large deviations, particularly the Gärtner–Ellis Theorem. Finally, we discuss Gibbs vs. Boltzmann/Einstein entropy in the choice of the quantum thermodynamic ensemble, as well as open problems. Full article

The idea of a canonical ensemble from Gibbs has been extended by Jean-Marie Souriau for a symplectic manifold where a Lie group has a Hamiltonian action. A novel symplectic thermodynamics and information geometry known as “Lie group thermodynamics” then explains foliation structures of thermodynamics. We then infer a geometric structure for heat equation from this archetypal model, and we have discovered a pure geometric structure of entropy, which characterizes entropy in coadjoint representation as an invariant Casimir function. The coadjoint orbits form the level sets on the entropy. By using the KKS 2-form in the affine case via Souriau’s cocycle, the method also enables the Fisher metric from information geometry for Lie groups. The fact that transverse dynamics to these symplectic leaves is dissipative, whilst dynamics along these symplectic leaves characterize non-dissipative phenomenon, can be used to interpret this Lie group thermodynamics within the context of an open system out of thermodynamics equilibrium. In the following section, we will discuss the dissipative symplectic model of heat and information through the Poisson transverse structure to the symplectic leaf of coadjoint orbits, which is based on the metriplectic bracket, which guarantees conservation of energy and non-decrease of entropy. Baptiste Coquinot recently developed a new foundation theory for dissipative brackets by taking a broad perspective from non-equilibrium thermodynamics. He did this by first considering more natural variables for building the bracket used in metriplectic flow and then by presenting a methodical approach to the development of the theory. By deriving a generic dissipative bracket from fundamental thermodynamic first principles, Baptiste Coquinot demonstrates that brackets for the dissipative part are entirely natural, just as Poisson brackets for the non-dissipative part are canonical for Hamiltonian dynamics. We shall investigate how the theory of dissipative brackets introduced by Paul Dirac for limited Hamiltonian systems relates to transverse structure. We shall investigate an alternative method to the metriplectic method based on Michel Saint Germain’s PhD research on the transverse Poisson structure. We will examine an alternative method to the metriplectic method based on the transverse Poisson structure, which Michel Saint-Germain studied for his PhD and was motivated by the key works of Fokko du Cloux. In continuation of Saint-Germain’s works, Hervé Sabourin highlights the, for transverse Poisson structures, polynomial nature to nilpotent adjoint orbits and demonstrated that the Casimir functions of the transverse Poisson structure that result from restriction to the Lie–Poisson structure transverse slice are Casimir functions independent of the transverse Poisson structure. He also demonstrated that, on the transverse slice, two polynomial Poisson structures to the symplectic leaf appear that have Casimir functions. The dissipative equation introduced by Lindblad, from the Hamiltonian Liouville equation operating on the quantum density matrix, will be applied to illustrate these previous models. For the Lindblad operator, the dissipative component has been described as the relative entropy gradient and the maximum entropy principle by Öttinger. It has been observed then that the Lindblad equation is a linear approximation of the metriplectic equation. Full article

Polyelectrolyte hydrogels can absorb a large amount of water across an osmotic membrane as a result of their swelling pressure. On the other hand, the insoluble cross-linked hydrogel network enables dewatering under the influence of external (thermal and/or mechanical) stimuli. Moreover, from a thermodynamic perspective, a polyelectrolyte hydrogel is already an osmotic membrane. These properties designate hydrogels as excellent candidates for use in desalination, at the same time avoiding the use of expensive membranes. In this article, we present our recent theoretical study of polyelectrolyte hydrogel usage for water desalination. Employing a coarse-grained model and the Gibbs ensemble, we modeled the thermodynamic equilibrium between the coexisting gel phase and the supernate aqueous salt solution phase. We performed a sequence of step-by-step hydrogel swellings and compressions in open and closed systems, i.e., in equilibrium with a large and with a comparably small reservoir of aqueous solution. The swelling in an open system removes ions from the large reservoir, whereas the compression in a closed system decreases the salt concentration in the small reservoir. We modeled this stepwise process of continuous decrease of water salinity from seawater up to freshwater concentrations and estimated the energy cost of the process to be comparable to that of reverse osmosis. Full article

We assess the degree of quantumness of the P, Q, and W quantum optics’ approximations in a thermal context governed by the canonical ensemble treatment. First, we remint the reader of the bridge connecting quantum optics with statistical mechanics using the abovementioned approximations at the temperature T. With the ensuing materials, we explore with some detail some features of the above bridge, related to the entropy and to thermal uncertainties. Some new relations concerning the degree of quantumness of the P, Q, and W are obtained by comparison between them and the exact and classical treatments. Full article

Rényi entropy was originally introduced in the field of information theory as a parametric relaxation of Shannon (in physics, Boltzmann–Gibbs) entropy. This has also fuelled different attempts to generalise statistical mechanics, although mostly skipping the physical arguments behind this entropy and instead tending to introduce it artificially. However, as we will show, modifications to the theory of statistical mechanics are needless to see how Rényi entropy automatically arises as the average rate of change of free energy over an ensemble at different temperatures. Moreover, this notion is extended by considering distributions for isospectral, non-isothermal processes, resulting in relative versions of free energy, in which the Kullback–Leibler divergence or the relative version of Rényi entropy appear within the structure of the corrections to free energy. These generalisations of free energy recover the ordinary thermodynamic potential whenever isothermal processes are considered. Full article