Gibbs ensembles in relativistic classical and quantum mechanics

Classical and quantum Gibbs ensembles are constructed for equilibrium statistical mechanics in the framework of an extension to many-body theory of a relativistic mechanics proposed by Stueckelberg. In addition to the usual chemical potential in the grand canonical ensemble, there is a new potential corresponding to the mass degree of freedom of relativistic systems. It is shown that in the nonrelativistic limit the relativistic ensembles we have obtained reduce to the usual ones, and mass fluctuations for the free-particle gas approach the fluctuations in N. The ultrarelativistic limit of the canonical ensemble for the free-particle gas differs from the corresponding limit of the ensemble proposed by Jüttner and Pauli. Due to the mass degree of freedom, the quantum counting of states is different from that of the nonrelativistic theory. If the mass distribution is sufficiently sharp, the thermodynamical effects of this multiplicity will not be large. There may, however, be detectable effects such as a shift in the Fermi level and the critical temperature for Bose-Einstein condensation, and some change in specific heats.     

Dynamical pair correlations of classical and quantum fluids perturbed with weak long-range forces

We study time dependent correlation functions of ideal classical and quantum gases using methods of equilibrium statistical mechanics. The basis for this is the path integral formalism of quantum mechanical systems. By this approach the statistical mechanics of a quantum mechanical system becomes the equivalent of a classical polymer problem in four dimensions where imaginary time is the fourth dimension. Several non-trivial results for quantum systems have been obtained earlier by this analogy. Here we will focus upon particle dynamics. First ideal gases are considered. Then interactions, that are assumed weak and of long range, are added, and methods of classical statistical mechanics are applied to obtain the leading contribution. Comparison is performed with known results of kinetic theory. These results demonstrate how methods developed for systems in thermal equilibrium also is applicable outside equilibrium. Thus, more generally, we have reason to expect that these methods will be accurate and useful for other situations of interacting many-body systems consisting of quantized particles too. To indicate so we sketch the computation of the induced Casimir force between parallel plates filled with ions for the situation where the ions are quantized, but the interaction remains electrostatic. Further in this respect we establish expressions for a leading correction to ab initio calculations for the energies of the quantized electrons of molecules. To our knowledge these two latter applications go beyond earlier results.     

Second quantized reduced Bloch equations and the exact solutions for pairing Hamiltonian

In this article, we present a set of hierarchy Bloch equations for the reduced density operators in either canonical or grand canonical ensembles in the occupation number representation. They provide a convenient tool for studying the equilibrium quantum statistical mechanics for some model systems. As an example of their applications, we solve the equations for the model system with a pairing Hamiltonian. With the aid of its symplectic group symmetry, we obtain the statistical reduced density matrices with different orders. As a special instance for the solutions, we also get the reduced density matrices of the ground state for a superconductor.     

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.     

Quantum statistical mechanics as a construction of an embedding scheme

The aim of the present paper is to show that the formalism of equilibrium quantum statistical mechanics can fully be incorporated into Ludwig's embedding scheme for classical theories in many-body quantum mechanics. A construction procedure based on a recently developed reconstruction procedure for the so-called macro-observable is presented which leads to the explicit determination of the set of classical ensembles compatible with the embedding scheme.     

Thermodynamics with generalized ensembles: The class of dual orthodes

We address the problem of the foundation of generalized ensembles in statistical physics. The approach is based on Boltzmann's concept of orthodes. These are the statistical ensembles that satisfy the heat theorem, according to which the heat exchanged divided by the temperature is an exact differential. This approach can be seen as a mechanical approach alternative to the well established information-theoretic one based on the maximization of generalized information entropy. Our starting point are the Tsallis escort ensembles which have been previously proved to be orthodes, and have been proved to interpolate between canonical and microcanonical ensembles. Here we shall see that the Tsallis escort ensembles belong to a wider class of orthodes that include the most diverse types of ensembles. All such ensembles admit both a microcanonical-like parametrization (via the energy), and a canonical-like one (via the parameter β). For this reason we name them “dual”. One central result used to build the theory is a generalized equipartition theorem. The theory is illustrated with a few examples and the equivalence of all the dual orthodes is discussed.     

Thermodynamic aspects of Schrödinger's probability relations

Using Schrödinger's generalized probability relations of quantum mechanics, it is possible to generate a canonical ensemble, the ensemble normally associated with thermodynamic equilibrium, by at least two methods, statistical mixing and subensemble selection, that do not involve thermodynamic equilibration. Thus the question arises as to whether an observer making measurements upon systems from a canonical ensemble can determine whether the systems were prepared by mixing, equilibration, or selection. Investigation of this issue exposes antinomies in quantum statistical thermodynamics. It is conjectured that resolution of these paradoxes may involve a new law of motion in quantum dynamics.     

A Canonical Ensemble Approach to the Fermion/Boson Random Point Processes and Its Applications

We introduce the boson and the fermion point processes from the elementary quantum mechanical point of view. That is, we consider quantum statistical mechanics of the canonical ensemble for a fixed number of particles which obey Bose-Einstein, Fermi-Dirac statistics, respectively, in a finite volume. Focusing on the distribution of positions of the particles, we have point processes of the fixed number of points in a bounded domain. By taking the thermodynamic limit such that the particle density converges to a finite value, the boson/fermion processes are obtained. This argument is a realization of the equivalence of ensembles, since resulting processes are considered to describe a grand canonical ensemble of points. Random point processes corresponding to para-particles of order two are discussed as an application of the formulation. Statistics of a system of composite particles at zero temperature are also considered as a model of determinantal random point processes.     

Hamiltonian Formulation of Statistical Ensembles and Mixed States of Quantum and Hybrid Systems

Representation of quantum states by statistical ensembles on the quantum phase space in the Hamiltonian form of quantum mechanics is analyzed. Various mathematical properties and some physical interpretations of the equivalence classes of ensembles representing a mixed quantum state in the Hamiltonian formulation are examined. In particular, non-uniqueness of the quantum phase space probability density associated with the quantum mixed state, Liouville dynamics of the probability densities and the possibility to represent the reduced states of bipartite systems by marginal distributions are discussed in detail. These considerations are used to study ensembles of hybrid quantum-classical systems. In particular, nonlinear evolution of a single hybrid system in a pure state and unequal evolutions of initially equivalent ensembles are discussed in the context of coupled hybrid systems.     

Thermodynamic theory of equilibrium fluctuations

The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.     

Constant pressure ensembles in statistical mechanics

A new statistical procedure is described for obtaining the thermodynamic properties of a molecular system directly as functions of the pressure. This procedure differs in principle from that suggested by Guggenheim [3] in that the members of the representative ensemble are envisaged as being in constant mechanical equilibrium with the exterior. The quantal and classical theories of petit micro-canonical and canonical ensembles of systems at constant pressure are presented, and shown to lead to the established results for perfect and imperfect gases, and for a hypothetical one-dimensional system. The conclusion that the statistical compressibility of a molecular system is essentially positive follows directly from the theory. An alternative procedure which leads to a more satisfactory form of Guggenheim's equation is also described, and its relation to the new approach is shown.     

The formalism of equilibrium quantum statistical mechanics revisited

It is shown that the traditional formalism of equilibrium quantum statistical mechanics may fully be incorporated into a general macro-observable approach to quantum statistical mechanics recently proposed by the same author. ^(1,2) In particular, the partition functions which in the traditional approach are assumed to connect nonnormalized density operators with thermodynamic functions are reinterpreted as functions connecting so-called quantum mechanical effect operators with state parameters. It is argued that these functions although only part of a much richer internal structure of the macro-observable are sufficient to cope with all problems one usually encounters in equilibrium quantum statistical mechanics. p]Denn eigentlich unternehmen wir umsonst, das Wesen eines Dinges auszudrücken. Wirkungen werden wir gewahr, und eine vollständige Geschichte dieser Wirkungen umfaßte wohl allenfalls das Wesen jenes Dinges. Johann W. v. Goethe Farbenlehre     

The canonical and grand canonical models for nuclear multifragmentation

Many observables seen in intermediate energy heavy-ion collisions can be explained on the basis of statistical equilibrium. Calculations based on statistical equilibrium can be implemented in microcanonical ensemble, canonical ensemble or grand canonical ensemble. This paper deals with calculations with canonical and grand canonical ensembles. A recursive relation developed recently allows calculations with arbitrary precision for many nuclear problems. Calculations are done to study the nature of phase transition in nuclear matter.     

Gibbs–Jaynes Entropy Versus Relative Entropy

The maximum entropy formalism developed by Jaynes determines the relevant ensemble in nonequilibrium statistical mechanics by maximising the entropy functional subject to the constraints imposed by the available information. We present an alternative derivation of the relevant ensemble based on the Kullback–Leibler divergence from equilibrium. If the equilibrium ensemble is already known, then calculation of the relevant ensemble is considerably simplified. The constraints must be chosen with care in order to avoid contradictions between the two alternative derivations. The relative entropy functional measures how much a distribution departs from equilibrium. Therefore, it provides a distinct approach to the calculation of statistical ensembles that might be applicable to situations in which the formalism presented by Jaynes performs poorly (such as non-ergodic dynamical systems).     

Equivalence of ensembles in quantum lattice systems: States

The general analysis of the equivalence of ensembles in quantum lattice systems, which was undertaken in paper I of this series, is continued.The properties of equilibrium states are considered in a variational sense. It is then shown that there exists a canonical as well as a microcanonical variational formulation of equilibrium both of which are equivalent to the grandcanonical formulation.Equilibrium states are constructed both in the canonical and in the microcanonical formalism by means of suitable limiting procedures.It is shown, in particular, that the invariant equilibrium states for a given energy and density are those for which the maximum of the mean entropy is reached. The mean entropy thus obtained coincides with the microcanonical entropy.     

Semiclassical expansion of quantum characteristics for many‐body potential scattering problem

In quantum mechanics, systems can be described in phase space in terms of the Wigner function and the star‐product operation. Quantum characteristics, which appear in the Heisenberg picture as the Weyl's symbols of operators of canonical coordinates and momenta, can be used to solve the evolution equations for symbols of other operators acting in the Hilbert space. To any fixed order in the Planck's constant, many‐body potential scattering problem simplifies to a statistical‐mechanical problem of computing an ensemble of quantum characteristics and their derivatives with respect to the initial canonical coordinates and momenta. The reduction to a system of ordinary differential equations pertains rigorously at any fixed order in ?. We present semiclassical expansion of quantum characteristics for many‐body scattering problem and provide tools for calculation of average values of time‐dependent physical observables and cross sections. The method of quantum characteristics admits the consistent incorporation of specific quantum effects, such as non‐locality and coherence in propagation of particles, into the semiclassical transport models. We formulate the principle of stationary action for quantum Hamilton's equations and give quantum‐mechanical extensions of the Liouville theorem on conservation of the phase‐space volume and the Poincaré theorem on conservation of 2p‐forms. The lowest order quantum corrections to the Kepler periodic orbits are constructed. These corrections show the resonance behavior.     

A new physical characterisation of classical systems in quantum mechanics

A physical characterisation of classical systems in quantum mechanics is given in terms of the set of ensembles in contrast to the well-known characterisations concerning the effects or observables: A quantum mechanical system is classical if and only if each two decompositions of every ensemble are compatible.