On the Distribution of the Wave Function for Systems in Thermal Equilibrium

For a quantum system, a density matrix ρ that is not pure can arise, via averaging, from a distribution μ of its wave function, a normalized vector belonging to its Hilbert space ?. While ρ itself does not determine a unique μ, additional facts, such as that the system has come to thermal equilibrium, might. It is thus not unreasonable to ask, which μ, if any, corresponds to a given thermodynamic ensemble? To answer this question we construct, for any given density matrix ρ, a natural measure on the unit sphere in ?, denoted GAP(ρ). We do this using a suitable projection of the Gaussian measure on ? with covariance ρ. We establish some nice properties of GAP(ρ) and show that this measure arises naturally when considering macroscopic systems. In particular, we argue that it is the most appropriate choice for systems in thermal equilibrium, described by the canonical ensemble density matrix ρ_β = (1/Z) exp (?β H). GAP(ρ) may also be relevant to quantum chaos and to the stochastic evolution of open quantum systems, where distributions on ? are often used.     

Baryon number projection for an interacting hadron gas

Calculations of hadronic matter usually enforce conservation of the average baryon number density using the grand canonical ensemble. We have performed calculations for an interacting system in the canonical ensemble with fixed baryon numberN _b , as appropriate for a finite fireball of the type produced in ultra relativistic heavy ion collisions. These results are compared with those obtained from calculations in the grand canonical ensemble. For an interacting nucleon gas the two ensembles yield free energies which differ by approximately 5%.     

Geometry of Lagrangian First-order Classical Field Theories

We construct a lagrangian geometric formulation for first-order field theories using the canonical structures of first-order jet bundles, which are taken as the phase spaces of the systems in consideration. First of all, we construct all the geometric structures associated with a first-order jet bundle and, using them, we develop the lagrangian formalism, defining the canonical forms associated with a lagrangian density and the density of lagrangian energy, obtaining the Euler-Lagrange equations in two equivalent ways: as the result of a variational problem and developing the jet field formalism (which is a formulation more similar to the case of mechanical systems). A statement and proof of Noether's theorem is also given, using the latter formalism.     

The inverse problem in classical statistical mechanics

We address the problem of whether there exists an external potential corresponding to a given equilibrium single particle density of a classical system. Results are established for both the canonical and grand canonical distributions. It is shown that for essentially all systems without hard core interactions, there is a unique external potential which produces any given density. The external potential is shown to be a continuous function of the density and, in certain cases, it is shown to be differentiable. As a consequence of the differentiability of the inverse map (which is established without reference to the hard core structure in the grand canonical ensemble), we prove the existence of the Ornstein-Zernike direct correlation function. A set of necessary, but not sufficient conditions for the solution of the inverse problem in systems with hard core interactions is derived.Work partially supported by NSF grant PHY-8117463Work partially supported by NSF grant PHY-8116101 A01     

Determination of the chemical potential and the energy of the ν=1/2 FQHE system for low temperatures

We consider the energy density of a spin polarized ν = 1/2 system for low temperatures. We show that due to the elimination of the magnetic field and the field of the positive background charge in the calculation of the grand canonical potential of Chern-Simons systems through a mean field formalism one gets corrections to the well known equations which determine the chemical potential and the energy from the grand canonical potential. We use these corrected equations to calculate the chemical potential and the energy of the ν = 1/2 system at low temperatures in two different approximations. Received 14 March 2001     

Density-functional theory of inhomogeneous fluids in the canonical ensemble

We present a density-functional approach for dealing with inhomogeneous fluids in the canonical ensemble. A general relation is proposed between the free-energy functionals in the canonical and the grand canonical ensembles. The minimization of the canonical-ensemble free-energy functional gives rise to Euler-Lagrange equations which involve averaged Ornstein-Zernike equations of second and third order. The theory is especially appropriate for systems with a small, fixed number of particles. As an example of application we obtain accurate results for the density profile of a hard-sphere fluid in a closed spherical cavity that contains only a few particles.     

The equivalence of ensembles for classical systems of particles

For systems of particles in classical phase space with standard Hamiltonian, we consider (spatially averaged) microcanonical Gibbs distributions in finite boxes. We show that infinite-volume limits along suitable subsequences exist and are grand canonical Gibbs measures. On the way, we establish a variational formula for the thermodynamic entropy density, as well as a variational characterization of grand canonical Gibbs measures.     

Ensemble Dependence of Fluctuations: Canonical Microcanonical Equivalence of Ensembles

We study the equivalence of microcanonical and canonical ensembles in continuous systems, in the sense of the convergence of the corresponding Gibbs measures and the first order corrections. We are particularly interested in extensive observables, like the total kinetic energy. This result is obtained by proving an Edgeworth expansion for the local central limit theorem for the energy in the canonical measure, and a corresponding local large deviations expansion. As an application we prove a formula due to Lebowitz–Percus–Verlet that express the asymptotic microcanonical variance of the kinetic energy in terms of the heat capacity.     

Gravitational phase transitions with an exclusion constraint in position space

We discuss the statistical mechanics of a system of self-gravitating particles with anexclusion constraint in position space in a space of dimension d. Theexclusion constraint puts an upper bound on the density of the system and can stabilize itagainst gravitational collapse. We plot the caloric curves giving the temperature as afunction of the energy and investigate the nature of phase transitions as a function ofthe size of the system and of the dimension of space in both microcanonical and canonicalensembles. We consider stable and metastable states and emphasize the importance of thelatter for systems with long-range interactions. For d ≤ 2, there is nophase transition. For d > 2, phase transitions can take place betweena “gaseous” phase unaffected by the exclusion constraint and a “condensed” phase dominatedby this constraint. The condensed configurations have a core-halo structure made of a“rocky core” surrounded by an “atmosphere”, similar to a giant gaseous planet. For largesystems there exist microcanonical and canonical first order phase transitions. Forintermediate systems, only canonical first order phase transitions are present. For smallsystems there is no phase transition at all. As a result, the phase diagram exhibits twocritical points, one in each ensemble. There also exist a region of negative specificheats and a situation of ensemble inequivalence for sufficiently large systems. We showthat a statistical equilibrium state exists for any values of energy and temperature inany dimension of space. This differs from the case of the self-gravitating Fermi gas forwhich there is no statistical equilibrium state at low energies and low temperatures whend ≥ 4. By a proper interpretation of the parameters, our results haveapplication for the chemotaxis of bacterial populations in biology described by ageneralized Keller-Segel model including an exclusion constraint in position space. Theyalso describe colloids at a fluid interface driven by attractive capillary interactionswhen there is an excluded volume around the particles. Connexions with two-dimensionalturbulence are also mentioned.     

Basic Brackets of a 2D Model for the Hodge Theory Without its Canonical Conjugate Momenta

We deduce the canonical brackets for a two (1+1)-dimensional (2D) free Abelian 1-form gauge theory by exploiting the beauty and strength of the continuous symmetries of a Becchi-Rouet-Stora-Tyutin (BRST) invariant Lagrangian density that respects, in totality, six continuous symmetries. These symmetries entail upon this model to become a field theoretic example of Hodge theory. Taken together, these symmetries enforce the existence of exactly the same canonical brackets amongst the creation and annihilation operators that are found to exist within the standard canonical quantization scheme. These creation and annihilation operators appear in the normal mode expansion of the basic fields of this theory. In other words, we provide an alternative to the canonical method of quantization for our present model of Hodge theory where the continuous internal symmetries play a decisive role. We conjecture that our method of quantization is valid for a class of field theories that are tractable physical examples for the Hodge theory. This statement is true in any arbitrary dimension of spacetime.     

Canonical hadron gas interpretation ofp-A E802 data

Hadron gas models have proved successful in predicting particle production in relativistic nucleus-nucleus collisions. The extension of these models to the smaller systems formed in proton-nucleus collisions requires that the finite size of the system be considered. We study two features introduced by the finite size: the need to conserve strangeness and baryon number exactly by performing calculations in the canonical ensemble, and the inclusion of a finite size geometrical correction term in the single particle density of states. We find significant differences between the grand canonical and canonical ensembles and a strong dependence on the baryon number of the system.     

Spin and the Thermal Equilibrium Distribution of Wave Functions

Consider a quantum system S weakly interacting with a very large but finite system B called the heat bath, and suppose that the composite S∪B is in a pure state Ψ with participating energies between E and E+δ with small δ. Then, it is known that for most Ψ the reduced density matrix of S is (approximately) equal to the canonical density matrix. That is, the reduced density matrix is universal in the sense that it depends only on S’s Hamiltonian and the temperature but not on B’s Hamiltonian, on the interaction Hamiltonian, or on the details of Ψ. It has also been pointed out that S can also be attributed a random wave function ψ whose probability distribution is universal in the same sense. This distribution is known as the “Scrooge measure” or “Gaussian adjusted projected (GAP) measure”; we regard it as the thermal equilibrium distribution of wave functions. The relevant concept of the wave function of a subsystem is known as the “conditional wave function.” In this paper, we develop analogous considerations for particles with spin. One can either use some kind of conditional wave function or, more naturally, the “conditional density matrix,” which is in general different from the reduced density matrix. We ask what the thermal equilibrium distribution of the conditional density matrix is, and find the answer that for most Ψ the conditional density matrix is (approximately) deterministic, in fact (approximately) equal to the canonical density matrix.     

High-Spin Nitrene Fine-Structure ESR Spectroscopy in Frozen Rigid Glasses: Exact Analytical Expressions for the Canonical Peaks and A D-Tensor Gradient Method for Line Broadening

In high-spin chemistry, random-orientation fine-structure electron paramagnetic resonance (FS ESR) spectroscopy holds the advantages of the most facile and convenient method to identify high-spin systems. The FS ESR spectroscopy for high spins in frozen rigid glasses has seemingly been well established since the first spin-quintet m-dicarbene and m-dinitrene appeared in 1967. The FS ESR spectra of organic quintet entities generated by photolysis in the 2-methyltetrahydrofuran (2-MTHF) glass, however, have never been fully analyzed due to a peculiar line broadening appearing at many canonical peaks. The line broadening has been a notorious obstacle that masks key FS transitions of many cases in organic glasses or argon matrices. We examine the origin of the line broadening, illustrating the comprehensive spectral analysis for m-dinitrenes and other types of typical quintet-state dinitrenes observed in the 2-MTHF glass. Our new approach to the line broadening analysis invokes both exact analytical solutions for the resonance fields of canonical peaks and a magnetic-parameter gradient method. We have derived the exact analytical expressions for FS canonical peaks for high-spin states, for the first time. A microscopic origin of the line broadening observed for high-spin nitrenes generated by photolysis in rigid glasses is proposed on the basis of quantum chemical calculations of the D-tensor.     

Two-dimensional Brownian vortices

We introduce a stochastic model of 2D Brownian vortices associated with the canonical ensemble. The point vortices evolve through their usual mutual advection but they experience in addition a random velocity and a systematic drift generated by the system as a whole. The statistical equilibrium state of this stochastic model is the Gibbs canonical distribution. We consider a single species system and a system made of two types of vortices with positive and negative circulations. At positive temperatures, like-sign vortices repel each other (“plasma” case) and at negative temperatures, like-sign vortices attract each other (“gravity” case). We derive the stochastic equation satisfied by the exact vorticity field and the Fokker-Planck equation satisfied by the N-body distribution function. We present the BBGKY-like hierarchy of equations satisfied by the reduced distribution functions and close the hierarchy by considering an expansion of the solutions in powers of 1/N, where N is the number of vortices, in a proper thermodynamic limit. For spatially inhomogeneous systems, we derive the kinetic equations satisfied by the smooth vorticity field in a mean field approximation valid for N→+∞. For spatially homogeneous systems, we study the two-body correlation function, in a Debye-Hückel approximation valid at the order O(1/N). The results of this paper can also apply to other systems of random walkers with long-range interactions such as self-gravitating Brownian particles and bacterial populations experiencing chemotaxis. Furthermore, for positive temperatures, our study provides a kinetic derivation, from microscopic stochastic processes, of the Debye-Hückel model of electrolytes.     

On the derivation of power-law distributions within classical statistical mechanics far from the thermodynamic limit

We show that within classical statistical mechanics, without taking the thermodynamic limit, the most general Boltzmann factor for the canonical ensemble is a q-exponential function. The only assumption here is that microcanonical distributions have to be separated from the total system energy, which is the prerequisite for any sensible measurement. We derive that all separable distributions are parametrized by a mathematical separation constant Q, which can be related to the non-extensivity q-parameter in Tsallis distributions. We further demonstrate that nature fixes the separation constant Q to 1 for large dimensionality of Gibbs $\Gamma$-phase space. Our results will be relevant for systems with a low-dimensional $\Gamma$-space, for example nanosystems, comprised of a small number of particles, or for systems with a dimensionally collapsed phase space, which might be the case for a large class of complex systems.     

Geometry of 2d spacetime and quantization of particle dynamics

We analyze classical and quantum dynamics of a relativistic particle in 2d spacetimes with constant curvature. We show that global symmetries of spacetime specify the symmetries of physical phase-space and the corresponding quantum theory. To quantize the systems we parametrize the physical phase-space by canonical coordinates. Canonical quantization leads to unitary irreducible representations of SO_↑(2.1) group.     

Ideal bose gas in an oscillator potential (exact solution)

Exact expressions for the statistical sum of the grand canonical ensemble and the one-particle density matrix are derived based on the definition of the density matrix for a system of N identical noninteracting Bose particles in an oscillator potential as a sum with respect to the symmetric exchange of the density matrix coordinates of distinguishable particles. A quasi-classical scenario is analyzed in detail.     

The Chemical Potential

The definition of the fundamental quantity, the chemical potential, is badly confused in the literature: there are at least three distinct definitions in various books and papers. While they all give the same result in the thermodynamic limit, major differences between them can occur for finite systems, in anomalous cases even for finite systems as large as a cm³. We resolve the situation by arguing that the chemical potential defined as the symbol μ conventionally appearing in the grand canonical density operator is the uniquely correct definition valid for all finite systems, the grand canonical ensemble being the only one of the various ensembles usually discussed (microcanonical, canonical, Gibbs, grand canonical) that is appropriate for statistical thermodynamics, whenever the chemical potential is physically relevant. The zero–temperature limit of this μ was derived by Perdew et al. for finite systems involving electrons, generally allowing for electron–electron interactions; we extend this derivation and, for semiconductors, we also consider the zero–T limit taken after the thermodynamic limit. The enormous finite size corrections (in macroscopic samples, e.g. 1 cm³) for one rather common definition of the c.p., found recently by Shegelski within the standard effective mass model of an ideal intrinsic semiconductor, are discussed. Also, two very–small–system examples are given, including a quantum dot.