Melting of embedded anisotropic particles: PbIn inclusions in Al

Small particles embedded in the solid state can assume facetted shapes that indicate the anisotropy in interfacial free energy between the particle and the embedding phase. Previous in situ transmission electron microscopy (TEM) of Al–In has shown that such facetted nanoparticles with cubic symmetry embedded in a solid can produce a series of complex melt configurations. To determine the dependence of melt configuration on solid–solid facet energies, this work numerically calculates the equilibrium melt trajectory for a family of cuboctahedral particles parameterized by the ratio of matrix–particle interfacial free energies for orientations taken with respect to the crystal axes of the matrix, ??=?γ₁₀₀/γ₁₁₁. The calculations assume that equilibrium occurs with the minimization of the total interfacial free energy to determine the stable internal melt configuration for a fixed volume of melt confined within a member of the cuboctahedral family. At particular melt volume fractions, abrupt transitions in shape occur when a stable configuration reaches a touching or necking instability. In situ TEM of a dilute Al alloy containing embedded nanosized PbIn inclusions that gradually melt as the temperature is increased from 230 to 260°C is consistent with the results calculated for ??=?1.245.     

Spin waves,vortices, and the structure of equilibrium states in the classicalXY model

We prove that, for spin systems with a continuous symmetry group on lattices of arbitrary dimension, the surface tension vanishes at all temperatures. For the classicalXY model in zero magnetic field, this result is shown to imply absence of interfaces in the thermodynamic limit, at arbitrary temperature. We show that, at values of the temperature at which the free energy of that model is continuously differentiable, i.e. at all except possibly countably many temperatures, there iseither aunique translation-invariant equilibrium state, or all such states are labelled by the elements of the symmetry group, SO(2). Moreover, there areno non-translation-invariant, but periodic equilibrium states. We also reconsider the representation of theXY model as a gas of spin waves and vortices and discuss the possibility that, in four or more dimensions, translation invariance may be broken by imposing boundary conditions which force an (open) vortex sheet through the system. Among our main tools are new correlation inequalities.     

Statistical mechanics of systems of unbounded spins

We develop the statistical mechanics of unboundedn-component spin systems on the latticeZ ^v interacting via potentials which are superstable and strongly tempered. We prove the existence and uniqueness of the infinite volume free energy density for a wide class of boundary conditions. The uniqueness of the equilibrium state (whose existence is established in general) is then proven for one component ferromagnetic spins whose free energy is differentiable with respect to the magnetic field.     

The Response of Glassy Systems to Random Perturbations: A Bridge Between Equilibrium and Off-Equilibrium

We discuss the response of aging systems with short-range interactions to a class of random perturbations. Although these systems are out of equilibrium, the limit value of the free energy at long times is equal to the equilibrium free energy. By exploiting this fact, we define a new order parameter function, and we relate it to the ratio between response and fluctuation, which is in principle measurable in an aging experiment. For a class of systems possessing stochastic stability, we show that this new order parameter function is intimately related to the static order parameter function, describing the distribution of overlaps between clustering states. The same method is applied to investigate the geometrical organization of pure states. We show that the ultrametric organization in the dynamics implies static ultrametricity, and we relate these properties to static separability, i.e., the property that the measure of the overlap between pure states is essentially unique. Our results, especially relevant for spin glasses, pave the way to an experimental determination of the order parameter function.     

Condensation in the Zero Range Process: Stationary and Dynamical Properties

The zero range process is of particular importance as a generic model for domain wall dynamics of one-dimensional systems far from equilibrium. We study this process in one dimension with rates which induce an effective attraction between particles. We rigorously prove that for the stationary probability measure there is a background phase at some critical density and for large system size essentially all excess particles accumulate at a single, randomly located site. Using random walk arguments supported by Monte Carlo simulations, we also study the dynamics of the clustering process with particular attention to the difference between symmetric and asymmetric jump rates. For the late stage of the clustering we derive an effective master equation, governing the occupation number at clustering sites.     

Equilibration,Generalized Equipartition,and Diffusion in Dynamical Lorentz Gases

We demonstrate approach to thermal equilibrium in the fully Hamiltonian evolution of a dynamical Lorentz gas, by which we mean an ensemble of particles moving through a d-dimensional array of fixed soft scatterers that each possess an internal harmonic or anharmonic degree of freedom to which moving particles locally couple. We analytically predict, and numerically confirm, that the momentum distribution of the moving particles approaches a Maxwell-Boltzmann distribution at a certain temperature T, provided that they are initially fast and the scatterers are in a sufficiently energetic but otherwise arbitrary stationary state of their free dynamics—they need not be in a state of thermal equilibrium. The temperature T to which the particles equilibrate obeys a generalized equipartition relation, in which the associated thermal energy k _B T is equal to an appropriately defined average of the scatterers’ kinetic energy. In the equilibrated state, particle motion is diffusive.     

Entropy and global Markov properties

We extend, refine and give simple proofs of some recent results on the validity of global Markov properties for classical spin systems. One of the new results is that there is a global Markov property that is satisfied by equilibrium states in general. The proof of this establishes formulas for the entropy and free energy that show that these quantities are, ford-dimensional systems, given in terms of (d–1)-dimensional systems. Furthermore, we show that global Markov properties imply the absence of some types of symmetry breaking.Research supported by NSF Grants DMS 85-12505 and SMR 86-12369     

Quantum Equilibrium Distributions of Displacements and Momenta of Particles in Molecules and Solids

The quantum equilibrium distribution, ?Qm, of an arbitrary number, m, of momentum or displacement components is determined for atoms that are part of a polyatomic molecule or a solid. This is shown to be a multidimensional Gaussian distribution. Two cases are considered: (1) the motion of the system as a whole is given, (2) it is in itself determined by the statistical equilibrium conditions. In the first case we obtain distributions for the vibrational momenta and displacements and in the second for the total momenta, including the momenta of vibrational, translational and rotational motions. The distributions for momenta and displacements of one particle and for the maximum number of linearly independent components of momenta and displacements of all particles of the system are considered as particular cases. It is shown that the averaging of any function, F_m, depending on an arbitrary number, m, of components of displacements or momenta of particles, over the canonical ensemble is reduced to the integration of this function weighted by ?Qm over all its arguments between infinite limits.     

The Dynamics of Electron Orbits during the Acceleration of Electrons in a Betatron

This paper presents a system of equations that describe the motion of charged particles in the electromagnetic field of a betatron. This system of equation was successfully used to study the behavior of the electron orbits and to determine the principal parameters of the electron beam in the electromagnetic field of a betatron during the electron acceleration and deceleration. The results of this study may find application in developing systems designed to accelerate electron beams. It has been shown that in the course of acceleration there is no damping of the betatron oscillations by the law B _z ^–1/2 and, correspondingly, no decrease in beam cross section. In contrast to the existing belief, the initial departure of the kinetic energy (momentum) of the injected electrons from the energy (momentum) of the electrons following the equilibrium orbit is not preserved in the course of acceleration. In the betatron chamber, the electron beam, when accelerated, does not constrict to form a ring but occupies a broad zone, whose dimensions are determined by the initial double amplitudes of the vertical and horizontal oscillations. Despite the large double amplitude of the oscillations of the beam particles, the average energy of the electrons differs from the energy of the electrons following the equilibrium orbit only slightly, and the departure of the average energy from the energy of the equilibrium electrons varies proportionally to the (varying) field of the betatron.     

Universality in some classical Coulomb systems of restricted dimension

Coulomb systems in which the particles interact through thed-dimensional Coulomb potential but are confined in a flat manifold of dimensiond–1 are considered. The actual Coulomb potential acting is defined by particular boundary conditions involving a characteristic macroscopic distanceW in the direction perpendicular to the manifold: either it is periodic of periodW in that direction, or it vanishes on one ideal conductor wall parallel to the manifold at a distanceW from it, or it vanishes on two parallel walls at a distanceW from each other with the manifold equidistant from them. Under the assumptions that classical equilibrium statistical mechanics is applicable and that the system has the macroscopic properties of a conductor, it is shown that the suitably smoothed charge correlation function is universal, and that the free energy and the grand potential have universal dependences onW (universal means independent of the microscopic detail). The casesd=2 are discussed in detail, and the generic results are checked on an exactly solvable model. The cased=3 of a plane parallel to an ideal conductor is also explicitly worked out.Laboratoire associé au Centre National de la Recherche Scientifique-URA D0063.     

Connecting Blackbody Radiation,Relativity, and Discrete Charge in Classical Electrodynamics

It is suggested that an understanding of blackbody radiation within classical physics requires the presence of classical electromagnetic zero-point radiation, the restriction to relativistic (Coulomb) scattering systems, and the use of discrete charge. The contrasting scaling properties of nonrelativistic classical mechanics and classical electrodynamics are noted, and it is emphasized that the solutions of classical electrodynamics found in nature involve constants which connect together the scales of length, time, and energy. Indeed, there are analogies between the electrostatic forces for groups of particles of discrete charge and the van der Waals forces in equilibrium thermal radiation. The differing Lorentz- or Galilean-transformation properties of the zero-point radiation spectrum and the Rayleigh-Jeans spectrum are noted in connection with their scaling properties. Also, the thermal effects of acceleration within classical electromagnetism are related to the existence of thermal equilibrium within a gravitational field. The unique scaling and phase-space properties of a discrete charge in the Coulomb potential suggest the possibility of an equilibrium between the zero-point radiation spectrum and matter which is universal (independent of the particle mass), and an equilibrium between a universal thermal radiation spectrum and matter where the matter phase space depends only upon the ratio mc ²/k _B T. The observations and qualitative suggestions made here run counter to the ideas of currently accepted quantum physics.     

Competition between pairing and deformation in finite Fermi systems

The problem of the possible deformation of finite Fermi systems with particle numbers of ≤10⁴ is studied within the Bardeen-Cooper-Schrieffer model. It is shown that for slight deformations of a spherical system consisting of one valence l shell (l ≫ 1), the results of the quasi-particle theory and the exact Richard- son theory virtually coincide. Analysis of the equilibrium deformation of a cluster shows that the system does not keep its spherical form even at a low number of valence particles.     

Fundamental functions in equilibrium thermodynamics

In the standard presentations of the principles of Gibbsian equilibrium thermodynamics one can find several gaps in the logic. For a subject that is as widely used as equilibrium thermodynamics, it is of interest to clear up such questions of mathematical rigor. In this paper it is shown that using convex analysis one can give a mathematically rigorous treatment of several basic aspects of equilibrium thermodynamics. On the basis of a fundamental convexity property implied by the second law, the following topics are discussed: thermodynamic stability, transformed fundamental functions (such as the Gibbs free energy), and the existence and uniqueness of possible final equilibrium states of closed composite thermodynamic systems. It is shown that a standard mathematical characterization of thermodynamic stability (involving a positive definiteness property) is sufficient but in fact not necessary for the physically superior convexity characterization of thermodynamic stability. Furthermore, it is found that functions such as the Gibbs free energy can be rigorously and globally defined using convex conjugation instead of Legendre transformation. Another result desribed in this paper is that equilibrium thermodynamics cannot always uniquely predict possible final equilibrium states of closed composite thermodynamic systems.     

Relativistic heavy-ion collisions: An approach based on non-equilibrium thermodynamics

A new theory of particle production in high energy collisions is proposed which is based on non-equilibrium thermodynamics. The non-equilibrium model is a major extension of the equilibrium thermodynamic model of relativistic heavy-ion collisions developed earlier. While the equilibrium thermodynamic theory is appropriate for the formation of light nuclei and for pions, the non-equilibrium theory applies to the creation of particles heavier than the pion, which include such particles as the strange mesons, strange baryons and the anti-nucleons. Using an approach based on the degree of the reaction of kinetic theory, the time evolution of the composition of hadronic systems in incomplete equilibrium is investigated. Densities of produced particles are related to space-time quantities and to the production cross sections of the underlying dynamic processes. An application of the non-equilibrium approach to the production of strange matter is given. The importance of secondary processes, following pion production, in the formation of strange matter is shown. In fact, the secondary production process for kaons is as important as the direct production process arising from initial nucleon-nucleon (NN) collision of a first collision picture. Thus, kaons can be produced in a late stage of the collision of two nuclei and they do not necessarily reflect the early stages of the collision as first thought. Using the experimental number of kaons, the time of reaction is also estimated. No evidence for a long-lived state of the nuclear system is found. Expressions for particle production ratios are developed. The results of an equilibrium theory and a non-equilibrium theory are found to be similar for such ratios. The chemical equilibrium constant is shown to be present in the non-equilibrium theory; the Boltzmann factor in the production threshold energy appears in the equilibrium theory. The K^?/K⁺ ratio is estimated. Surprisingly, reasonable agreement with experiment is found in the K^?/K⁺ ratio using the equilibrium theory, even though the production processes for K⁺'s and K^?'s treated individually, are not ones for which the equilibrium theory applies. It is shown that a fundamental difference between the equilibrium and non-equilibrium theory is lost when particle ratios for non-equilibrium particles are taken. Expressions for the production of complex composite structures made of strange particles are developed. The non-equilibrium model with some modifications may be useful for high energy NN and pion-nucleon collisions.     

Active Brownian motion models and applications to ratchets

We give an overview over recent studies on the model of Active Brownian Motion (ABM) coupled to reservoirs providing free energy which may be converted into kinetic energy of motion. First, we present an introduction to a general concept of active Brownian particles which are capable to take up energy from the source and transform part of it in order to perform various activities. In the second part of our presentation we consider applications of ABM to ratchet systems with different forms of differentiable potentials. Both analytical and numerical evaluations are discussed for three cases of sinusoidal, staircaselike and Mateos ratchet potentials, also with the additional loads modelled by tilted potential structure. In addition, stochastic character of the kinetics is investigated by considering perturbation by Gaussian white noise which is shown to be responsible for driving the directionality of the asymptotic flux in the ratchet. This stochastically driven directionality effect is visualized as a strong nonmonotonic dependence of the statistics of the right versus left trajectories of motion leading to a net current of particles. Possible applications of the ratchet systems to molecular motors are also briefly discussed.     

Partial-wave Scattering and Statistical Mechanics via the l-wave Non-local Separable Potential of Rank-two

The equilibrium statistical mechanics relations are shown to be related to T-matrix, which describes the scattering processes taking place in the thermodynamic system consisting of free particles and independent correlated pairs, interacting via the separable non-local potential of rank two in the ℓth partial wave. Thermodynamic properties are related to the correlated states, when making a pole expansion of the analytically continued momentum matrix element of R _ℓ (z), the difference between the resolvents of the interacting and free Hamiltonians. It is shown that local potentials equivalent to the nonlocal ones have an attractive part which is responsible for a bound state and negative values of some thermodynamic properties.     

Nonequilibrium thermofield dynamics

The dissipative effects in nonequilibrium thermodfield dynamics are the gauge fields of theSU(1, 1) symmetry of the free bosonic thermal theory [SU(2) for the fermionic one]. In two dimensions some nonequilibrium systems are equivalent to equilibrium systems. An interesting relation exists between the equivalence principle of general relativity and the assumption, in statistical mechanics, of the existence of local subsystems in equilibrium.     

Accumulation of Particles and Formation of a Dissipative Structure in a Nonequilibrium Bath

The standard textbooks contain good explanations of how and why equilibrium thermodynamics emerges in a reservoir with particles that are subjected to Gaussian noise. However, in systems that convert or transport energy, the noise is often not Gaussian. Instead, displacements exhibit an α-stable distribution. Such noise is commonly called Lévy noise. With such noise, we see a thermodynamics that deviates from what traditional equilibrium theory stipulates. In addition, with particles that can propel themselves, so-called active particles, we find that the rules of equilibrium thermodynamics no longer apply. No general nonequilibrium thermodynamic theory is available and understanding is often ad hoc. We study a system with overdamped particles that are subjected to Lévy noise. We pick a system with a geometry that leads to concise formulae to describe the accumulation of particles in a cavity. The nonhomogeneous distribution of particles can be seen as a dissipative structure, i.e., a lower-entropy steady state that allows for throughput of energy and concurrent production of entropy. After the mechanism that maintains nonequilibrium is switched off, the relaxation back to homogeneity represents an increase in entropy and a decrease of free energy. For our setup we can analytically connect the nonequilibrium noise and active particle behavior to entropy decrease and energy buildup with simple and intuitive formulae.     

Collective Multipole Expansions and the Perturbation Theory in the Quantum Three-Body Problem

The perturbation theory with respect to the potential energy of three particles is considered. The first-order correction to the continuum wave function of three free particles is derived. It is shown that the use of the collective multipole expansion of the free three-body Green function over the set of Wigner D-functions can reduce the dimensionality of perturbative matrix elements from twelve to six. The explicit expressions for the coefficients of the collective multipole expansion of the free Green function are derived. It is found that the S-wave multipole coefficient depends only upon three variables instead of six as higher multipoles do. The possible applications of the developed theory to the three-body molecular break-up processes are discussed.     

Brownian dynamics of polydisperse colloidal hard spheres: Equilibrium structures and random close packings

Recently we presented a new technique for numerical simulations of colloidal hard-sphere systems and showed its high efficiency. Here, we extend our calculations to the treatment of both 2- and 3-dimensional monodisperse and 3-dimensional polydisperse systems (with sampled finite Gaussian size distribution of particle radii), focusing on equilibrium pair distribution functions and structure factors as well as volume fractions of random close packing (RCP). The latter were determined using in principle the same technique as Woodcock or Stillinger had used. Results for the monodisperse 3-dimensional system show very good agreement compared to both pair distribution and structure factor predicted by the Percus-Yevick approximation for the fluid state (volume fractions up to 0.50). We were not able to find crystalline 3d systems at volume fractions 0.50–0.58 as shown by former simulations of Reeet al. or experiments of Pusey and van Megen, due to the fact that we used random start configurations and no constraints of particle positions as in the cell model of Hoover and Ree, and effects of the overall entropy of the system, responsible for the melting and freezing phase transitions, are neglected in our calculations. Nevertheless, we obtained reasonable results concerning concentration-dependent long-time selfdiffusion coefficients (as shown before) and equilibrium structure of samples in the fluid state, and the determination of the volume fraction of random close packing (RCP, glassy state). As expected, polydispersity increases the respective volume fraction of RCP due to the decrease in free volume by the fraction of the smaller spheres which fill gaps between the larger particles.