Large Deviation Principles and Complete Equivalence and Nonequivalence Results for Pure and Mixed Ensembles

We consider a general class of statistical mechanical models of coherent structures in turbulence, which includes models of two-dimensional fluid motion, quasi-geostrophic flows, and dispersive waves. First, large deviation principles are proved for the canonical ensemble and the microcanonical ensemble. For each ensemble the set of equilibrium macrostates is defined as the set on which the corresponding rate function attains its minimum of 0. We then present complete equivalence and nonequivalence results at the level of equilibrium macrostates for the two ensembles. Microcanonical equilibrium macrostates are characterized as the solutions of a certain constrained minimization problem, while canonical equilibrium macrostates are characterized as the solutions of an unconstrained minimization problem in which the constraint in the first problem is replaced by a Lagrange multiplier. The analysis of equivalence and nonequivalence of ensembles reduces to the following question in global optimization. What are the relationships between the set of solutions of the constrained minimization problem that characterizes microcanonical equilibrium macrostates and the set of solutions of the unconstrained minimization problem that characterizes canonical equilibrium macrostates? In general terms, our main result is that a necessary and sufficient condition for equivalence of ensembles to hold at the level of equilibrium macrostates is that it holds at the level of thermodynamic functions, which is the case if and only if the microcanonical entropy is concave. The necessity of this condition is new and has the following striking formulation. If the microcanonical entropy is not concave at some value of its argument, then the ensembles are nonequivalent in the sense that the corresponding set of microcanonical equilibrium macrostates is disjoint from any set of canonical equilibrium macrostates. We point out a number of models of physical interest in which nonconcave microcanonical entropies arise. We also introduce a new class of ensembles called mixed ensembles, obtained by treating a subset of the dynamical invariants canonically and the complementary set microcanonically. Such ensembles arise naturally in applications where there are several independent dynamical invariants, including models of dispersive waves for the nonlinear Schrödinger equation. Complete equivalence and nonequivalence results are presented at the level of equilibrium macrostates for the pure canonical, the pure microcanonical, and the mixed ensembles.     

The Generalized Canonical Ensemble and Its Universal Equivalence with the Microcanonical Ensemble

This paper shows for a general class of statistical mechanical models that when the microcanonical and canonical ensembles are nonequivalent on a subset of values of the energy, there often exists a generalized canonical ensemble that satisfies a strong form of equivalence with the microcanonical ensemble that we call universal equivalence. The generalized canonical ensemble that we consider is obtained from the standard canonical ensemble by adding an exponential factor involving a continuous function g of the Hamiltonian. For example, if the microcanonical entropy is C², then universal equivalence of ensembles holds with g taken from a class of quadratic functions, giving rise to a generalized canonical ensemble known in the literature as the Gaussian ensemble. This use of functions g to obtain ensemble equivalence is a counterpart to the use of penalty functions and augmented Lagrangians in global optimization. linebreak Generalizing the paper by Ellis et al. [J. Stat. Phys. 101:999–1064 (2000)], we analyze the equivalence of the microcanonical and generalized canonical ensembles both at the level of equilibrium macrostates and at the thermodynamic level. A neat but not quite precise statement of one of our main results is that the microcanonical and generalized canonical ensembles are equivalent at the level of equilibrium macrostates if and only if they are equivalent at the thermodynamic level, which is the case if and only if the generalized microcanonical entropy s–g is concave. This generalizes the work of Ellis et al., who basically proved that the microcanonical and canonical ensembles are equivalent at the level of equilibrium macrostates if and only if they are equivalent at the thermodynamic level, which is the case if and only if the microcanonical entropy s is concave.     

The equivalence of ensembles for lattice systems: Some examples and a counterexample

We describe the problem of the equivalence of ensembles at the level of states for classical lattice systems. We discuss circumstances where the vanishing of the specific information gain of a sequence of microcanonical measures with respect to a sequence of grand canonical measures implies the equivalence of ensembles. We give a simple derivation of a criterion for the vanishing of the specific information gain in terms of thermodynamic functions. The proof uses ideas from the theory of large deviations but is self-contained. We show how the criterion works in a simple model of a paramagnet and in the Ising model of a ferromagnet in any dimension but fails in the case of the Curie-Weiss mean-field model.     

Quenched Large Deviation Principle for the Overlap of a p-Spins System

In this note, we prove a quenched large deviation result for the overlap of a p-spins interaction system at high temperature. The rate function of the large deviation principle is proved to be deterministic, and some of its basic properties are studied. Our result is based on a pure state result for a multidimensional p-spins system combined with a careful application of the Gärtner–Ellis Theorem     

Statistical Physics on the Space (x, v) for Dissipative Systems and Study of an Ensemble of Harmonic Oscillators in a Weak Linear Dissipative Medium

We use the phase space position-velocity (x, v) to deal with the statistical properties of velocity dependent dynamical systems, like dissipative ones. Within this approach, we study the statistical properties of an ensemble of harmonic oscillators in a linear weak dissipative media. Using the Debye model of a crystal, we calculate at first order in the dissipative parameter the entropy, free energy, internal energy, equation of state and specific heat using the classical and quantum approaches. For the classical approach we found that the entropy, the equation of state, and the free energy depend on the dissipative parameter, but the internal energy and specific heat do not depend of it. For the quantum case, we found that all the thermodynamical quantities depend on this parameter. PACS: 05.20.Gg, 05.30.Ch, 05.20.-y, 05.30.-d     

Relationship between the diffusion rate constant and rate constant of triplet-triplet annihilation for porphyrins in liquid solutions

Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70. F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 63, No. 4, pp. 613–621, July–August, 1996.     

Application of the method of X-ray fluorescence analysis for determination of the degree of chlorination of copper phthalocyanin

To whom correspondence should be addressd.     

On the number of invariant measures for higher-dimensional chaotic transformations

LetS be a bounded region inR ^N and letP={S _l } _i=1 ^m be a partition ofS into a finite number of closed subsets having piecewiseC ² boundaries of finite (N–1)-dimensional measure. Let :SS be piecewiseC ² onP and expanding in the sense that there exists 0<<1 such that for anyi=1,2,...,m, DT _i ^–1<, whereDT _i ^–1 is the derivative matrix ofT _i ^–1 and · is the Euclidean matrix norm. We prove that for some classes of such mappings, for example, Jabtonski transformations or convexity-preserving transformations, the number of crossing points constitutes a bound for the number of ergodic absolutely continuous -invariant measures. We give examples showing that in general the simple bound of one-dimensional dynamics cannot be generalized to higher dimensions. In fact, we show that it is possible to construct piecewise expandingC ² transformations on a fixed partition with a finite number of elements but which have an arbitrarily large number of ergodic, absolutely continuous invariant measures.     

A solution of the DGLAP equation for gluon at low x

We obtain a solution of the DGLAP equation for the gluon at low x first by expanding the gluon in a Taylor series and then using the method of characteristics. We test its validity by comparing it with that of Glück, Reya and Vogt. The convergence criteria of the approximation used are also discussed. We also calculate εF ₂(x,Q)²/ε In Q ² using its approximate relations with the gluon distribution at low x. The predictions are then compared with the HERA data.     

Decays of excited baryons in the large- N<Subscript>c</Subscript> expansion of QCD

We present the analysis of the decay widths of excited baryons in the framework of the 1/N _c expansion of QCD. These studies are performed up to order 1/N _c and include both positive- and negative-parity excited baryons.     

Pion mass dependence of the nucleon mass in the chiral quark soliton model

The dependence of the nucleon mass on the mass of the pion is studied in the framework of the chiral quark-soliton model. A remarkable agreement is observed with lattice data from recent full dynamical simulations. The possibility and limitations to use the results from the chiral quark soliton model as a guideline for the chiral extrapolation of lattice data are discussed.     

Comparison of Theoretical Methods and Basis Sets for ab initio and DFT Calculations of the Structure and Frequencies of Normal Vibrations of Polyatomic Molecules

The dependence of the quality of calculation of the geometric parameters and frequencies of normal vibrations on the choice of the theoretical method and the basis set of Gaussian functions has been investigated within the framework of four approximations (DFT/B3LYP, HF, MP2, MP3), using benzene and s-triazine molecules as an example. It has been shown that the molecular parameters calculated using the basis set without polarization functions within the framework of any of the above theoretical methods agree poorly with the experimental data. It has been concluded that the use of the basis set 6-31G(d) within the framework of these methods with allowance for the electron correlation for calculating the geometric parameters and frequencies of normal vibrations of polyatomic cyclic compounds is most optimum in terms of the relation between the expenditure of time and the quality of the calculation. The coefficients of linear scaling of frequencies have been obtained by the DFT/B3LYP method for 22 basis sets that were tested on porphin, pyrrole, indene, and pyridine molecules. Atypically large errors in determining the frequencies of some benzene and s-triazine vibrations have been obtained in a number of quantum-mechanical calculations with large basis sets. The changes in the force field for these cases have been investigated with the example of the benzene molecule.     

Nature of the axial-vector mesons from their N<Subscript>c</Subscript> behavior within the chiral unitary approach

By describing within the chiral unitary approach the s -wave interaction of the vector meson nonet with the octet of pseudoscalar Goldstone bosons, we find that the main component of the axial-vector mesons --b ₁(1235) , h ₁(1170) , h ₁(1380) , a ₁(1260) , f ₁(1285) and the two states associated to the K ₁(1270) -- does not follow the QCD dependence on the number of colors for ordinary q mesons.     

Extraction of radiative decay width for the non-strange partner of Θ

Using the results of the GRAAL Collaboration on the η photoproduction from the neutron target, we attempt to extract the partial radiative width of the possible new nucleon resonance N ^*(1675). The obtained estimates support this resonance to be a very attractive candidate for the non-strange member of the exotic antidecuplet of baryons --a partner of the Θ⁺ pentaquark. Our phenomenological value for the transition magnetic moment μ(n ^* n), appears to be in good agreement with the predictions of the Chiral Quark Soliton Model.     

Loop Observables for BF Theories in Any Dimension and the Cohomology of Knots

A generalization of Wilson loop observables for BF theories in any dimension is introduced within the Batalin–Vilkovisky framework. The expectation values of these observables are cohomology classes of the space of imbeddings of a circle. One of the resulting theories discussed in the Letter has only trivalent interactions and, irrespective of the actual dimension, looks like a three-dimensional Chern–Simons theory.