Microcanonical scaling in small systems

A microcanonical finite-size scaling ansatz is discussed. It exploits the existence of a well-defined transition point for systems of finite size in the microcanonical ensemble. The best data collapse obtained for small systems yields values for the critical exponents in good agreement with other approaches. The exact location of the infinite system critical point is not needed when extracting critical exponents from the microcanonical finite-size scaling theory.     

Phase transitions in small systems: Microcanonical vs. canonical ensembles

We compare phase transition(-like) phenomena in small model systems for both microcanonical and canonical ensembles. The model systems correspond to a few classical (non-quantum) point particles confined in a one-dimensional box and interacting via Lennard-Jones-type pair potentials. By means of these simple examples it can be shown already that the microcanonical thermodynamic functions of a small system may exhibit rich oscillatory behavior and, in particular, singularities (non-analyticities) separating different microscopic phases. These microscopic phases may be identified as different microphysical dissociation states of the small system. The microscopic oscillations of microcanonical thermodynamic quantities (e.g., temperature, heat capacity, or pressure) should in principle be observable in suitably designed evaporation/dissociation experiments (which must realize the physical preconditions of the microcanonical ensemble). By contrast, singular phase transitions cannot occur, if a small system is embedded into an infinite heat bath (thermostat), corresponding to the canonical ensemble. For the simple model systems under consideration, it is nevertheless possible to identify a smooth canonical phase transition by studying the distribution of complex zeros of the canonical partition function.     

An Alternative Derivation of Quantum Mechanical Transition State Reaction Rate Theory

The quantum mechanical transition state reaction rates for both microcanonical and macrocanonical expressions are derived from a recently developed classical reaction rate theory. The newly derived quantum transition-state-like rates are good for both unimolecular reaction and bimolecular reaction depending on the choices of the transition state dividing surfaces. In a special choice of the transition dividing surface for bimolecular reaction, the macrocanonic rate derived in this paper is reduced to the flux-flux autocorrelation formalism derived from quantum bimolecular reactive scattering by Miller and to those obtained by Yamamo to using Ku to linear response an alysis.     

Extended gaussian ensemble solution and tricritical points of a system with long-range interactions

The gaussian ensemble and its extended version theoretically play the important role of interpolating ensembles between the microcanonical and the canonical ensembles. Here, the thermodynamic properties yielded by the extended gaussian ensemble (EGE) for the Blume-Capel (BC) model with infinite-range interactions are analyzed. This model presents different predictions for the first-order phase transition line according to the microcanonical and canonical ensembles. From the EGE approach, we explicitly work out the analytical microcanonical solution. Moreover, the general EGE solution allows one to illustrate in details how the stable microcanonical states are continuously recovered as the gaussian parameter γ is increased. We found out that it is not necessary to take the theoretically expected limit γ → ∞ to recover the microcanonical states in the region between the canonical and microcanonical tricritical points of the phase diagram. By analyzing the entropy as a function of the magnetization we realize the existence of unaccessible magnetic states as the energy is lowered, leading to a breaking of ergodicity.     

ON THE BEHAVIOR OF PHASE TRANSITION SHOWN IN DISASSYMBLY PROCESSES OF VERY HOT AND DILUTE FINITE NUCLEAR SYSTEMS

The behaviors of phase transition shown in disassymbly processes of very hot and dilute finite nuclear system have been exposed by using canonical (microcanonical) ensemble Monte Carlo simulation.It is explained that they result from the competition between Coulomb interaction and the effect of finiteness.     

Microcanonical analyses of peptide aggregation processes

We propose the use of microcanonical analyses for numerical studies of peptide aggregation transitions. Performing multicanonical Monte Carlo simulations of a simple hydrophobic-polar continuum model for interacting heteropolymers of finite length, we find that the microcanonical entropy behaves convex in the transition region, leading to a negative microcanonical specific heat. As this effect is also seen in first-order-like transitions of other finite systems, our results provide clear evidence for recent hints that the characterization of phase separation in first-order-like transitions of finite systems profits from this microcanonical view.     

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.     

Interference and diffraction effects in folding mirror schlieren diffraction interferometer

Experimental investigations on interference and diffraction phenomenon occurring in a folding mirror schlieren diffraction interferometer have been presented. It is shown that the well-known Lloyd mirror interferometer can easily be converted into a folding mirror schlieren diffraction interferometer. Various intermediate stages occur as the basic two-beam interference pattern in Lloyd mirror interferometer is transformed into a schlieren diffraction pattern. Study of these intermediate stages gives a good insight in understanding the transition behaviour between the fundamental phenomenon of interference and diffraction taking place as the mirror-edge approaches the Airy disk.     

Microcanonical Phase Diagram of the BEG and Ising Models

The density of states of long-range Blume-Emery-Griffiths (BEG) and short-range Ising models are obtained by using Wang-Landau sampling with adaptive windows in energy and magnetization space. With accurate density of states, we are able to calculate the microcanonical specific heat of fixed magnetization introduced by Kastner et al. in the regions of positive and negative temperature. The microcanonical phase diagram of the Ising model shows a continuous phase transition at a negative temperature in energy and magnetization plane. However the phase diagram of the long-range model constructed by peaks of the microcanonical specific heat looks obviously different from the Ising chart.     

Microcanonical Phase Diagram of the BEG and Ising Models

The density of states of long-range Blume-Emery-Griffiths(BEG) and short-range Ising models are obtained by using Wang-Landau sampling with adaptive windows in energy and magnetization space.With accurate density of states,we are able to calculate the microcanonical specific heat of fixed magnetization introduced by Kastner et al.in the regions of positive and negative temperature.The microcanonical phase diagram of the Ising model shows a continuous phase transition at a negative temperature in energy and magnetization plane.However the phase diagram of the long-range model constructed by peaks of the microcanonical specific heat looks obviously different from the Ising chart.     

Heat capacity of isolated clusters

The character of interaction between thermal (vibrational) and configurational cluster excitations is considered under adiabatic conditions when a cluster is a member of a microcanonical ensemble. The hierarchy of equilibration times determines the character of atomic equilibrium in the cluster. The behavior of atoms in the cluster can be characterized by two effective (mean) temperatures, corresponding to the solid and liquid aggregate states, because the typical time for equilibration of atomic motion is less than the transition time between aggregate states. If the cluster is considered for a time much longer than the typical dwell time in either phase, then it is convenient to characterize the system by only one temperature, which is determined from the statistical-thermodynamic long-time average. These three temperatures are not far apart, nor are the cluster heat capacities evaluated on the basis of these definitions of temperature. The heat capacity of a microcanonical ensemble may be negative for two coexisting phases if the mean temperature is defined in terms of the mean kinetic energy, rather than as the derivative of energy with respect to microcanonical entropy. However, if the configurational excitation energy is smaller than the total excitation energy separating the phases, then the two-state model predicts a positive heat capacity under either definition of temperature. Moreover, if the cluster is sufficiently large, then the maximum values of the microcanonical and canonical heat capacities are equal.     

The equivalence of ensembles and the Gibbs phase rule for classical lattice systems

We study the relation between the microcanonical, canonical, and grand canonical ensembles in the thermodynamic limit when the system becomes infinite. They are equivalent if there is only one phase in the system. In general it is shown that there is a unique limit of the microcanonical state being a mixture of pure phases if the microcanonical restrictions determine the volume fractions of the phases uniquely, and then the Gibbs phase rule is valid. In this context we show how to define the set of order parameters associated with the state of the system in a natural way.     

Statistical hadronization and hadronic microcanonical ensemble I

We present a full treatment of the microcanonical ensemble of the ideal hadron-resonance gas starting from a quantum-mechanical formulation which is appropriate for the statistical model of hadronization. By using a suitable transition operator for hadronization we are able to recover the results of the statistical theory, particularly the expressions of the rates of different channels. Explicit formulae are obtained for the phase space volume or density of states of the ideal relativistic gas in quantum statistics as a cluster decomposition, generalizing previous ones in the literature. The problem of the computation of averages in the hadron gas microcanonical ensemble and the comparison with canonical ones will be the main subject of a forthcoming second paper.Received: 8 July 2003, Revised: 17 October 2003, Published online: 5 May 2004     

Caloric curves and energy fluctuations in the microcanonical liquid-Gas phase transition

In this paper we study a microcanonical lattice gas model with a constrained average volume. We show that the caloric curve explicitly depends on the considered transformation of the volume with the excitation energy and so does not bear direct information on the characteristics of the phase transition. Conversely, partial energy fluctuations are demonstrated to be a direct measure of the equation of state. Since the heat capacity has a negative branch in the phase transition region, the presence of abnormally large kinetic energy fluctuations is a signal of the liquid-gas phase transition.     

Quantum microcanonical entropy of a pair of observables

The quantum analogue of the classical theory of the joint microcanonical entropy of a pair of observables is investigated for a system of a large number of identical non-interacting subsystems. It is shown that the quantum joint entropy coincides with the classical joint entropy of an appropriately chosen auxiliary classical system, and known results for classical systems are applied to prove the equivalence of the quantum microcanonical and quantum canonical ensembles.     

Microcanonical Analysis on a System with Long-Range Interactions

We study a long-range interacting spin chain placed in a staggered magnetic field using microcanonical approach and obtain the global phase diagram. We find that this model exhibits both first order phase transition and second order phase transition separated by a tricritical point, and temperature jump can be observed in the first order phase transition.     

Negative heat capacity for a cluster of 147 sodium atoms

There exists a surprising theoretical prediction for a small system: its microcanonical heat capacity can become negative. An increase of energy can-under certain conditions-lead to a lower temperature. Here we present experimental evidence that a cluster containing exactly 147 sodium atoms does indeed have a negative microcanonical heat capacity near its solid to liquid transition.     

Microcanonical equilibrium properties of chiral liquid crystals—a Monte Carlo study

Chiral liquid crystals have been investigated by means of a multicanonical Monte Carlo approach in order to characterize their phase behaviour by microcanonical equilibrium properties. The liquid crystals were described by three-dimensional lattice systems with intermolecular interactions given by the chiral Lebwohl-Lasher potential. Self-determined boundary conditions have been applied in order to enable the formation of chiral phases with equilibrium pitch. Selected thermodynamic properties, e.g. microcanonical entropy, temperature, heat capacity and a set of order parameters have been determined with dependence on microcanonical total energy. A cholesteric phase with temperature-induced helix inversion could be proven where the helical superstructure of the single component system studied changed its handedness through an infinite-pitch system. The thermodynamical behaviour in the microcanonical ensemble was found to be very similar to the behaviour in the canonical ensemble. The study of microcanonical equilibrium properties by means of multicanonical Monte Carlo simulations was shown to be a powerful tool for the study of the phase behaviour of model liquid crystals.     

Nonanalyticities of entropy functions of finite and infinite systems

In contrast to the canonical ensemble where thermodynamic functions are smooth for all finite system sizes, the microcanonical entropy can show nonanalytic points also for finite systems. The relation between finite and infinite system nonanalyticities is illustrated by means of a simple classical spinlike model which is exactly solvable for both finite and infinite system sizes, showing a phase transition in the latter case. The microcanonical entropy is found to have exactly one nonanalytic point in the interior of its domain. For all finite system sizes, this point is located at the same fixed energy value epsilon(c)(finite), jumping discontinuously to a different value epsilon(c)(infinite) in the thermodynamic limit. Remarkably, epsilon(c)(finite) equals the average potential energy of the infinite system at the phase transition point. The result indicates that care is required when trying to infer infinite system properties from finite system nonanalyticities.     

Partial equivalence of statistical ensembles and kinetic energy

The phenomenon of partial equivalence of statistical ensembles is illustrated by discussing two examples, the mean-field XY and the mean-field spherical model. The configurational parts of these systems exhibit partial equivalence of the microcanonical and the canonical ensemble. Furthermore, the configurational microcanonical entropy is a smooth function, whereas a nonanalytic point of the configurational free energy indicates the presence of a phase transition in the canonical ensemble. In the presence of a standard kinetic energy contribution, partial equivalence is removed and a nonanalyticity arises also microcanonically. Hence in contrast to the common belief, kinetic energy, even though a quadratic form in the momenta, has a nontrivial effect on the thermodynamic behaviour. As a by-product we present the microcanonical solution of the mean-field spherical model with kinetic energy for finite and infinite system sizes.