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.     

Molecular dynamics and time reversibility

We present a time-symmetrical integer arithmetic algorithm for numerical (molecular dynamics) simulations of classical fluids. This algorithm is used to illustrate, through concrete examples, that time-asymmetric evolutions are typical for systems of many particles evolving according to reversible microscopic dynamics and to calculate the asymptotic behavior of the velocity autocorrelation function with an improved accuracy. The equivalence between equilibrium time averages and microcanonical ensemble averages is checked via two new sampling methods for computing microcanonical averages of classical systems.     

Ensemble properties and molecular dynamics of unstable systems

The Hertel-Thirring cell model for unstable systems (of purely attractive particles) is solved in the canonical ensemble for arbitrary dimensions. The differences between the phase transitions found in the canonical and in the microcanonical ensemble are discussed. The cluster phase (with a complete collapse in the ground state) exhibits the nonextensive character of the cell model. The results of the cell model are compared with molecular-dynamics simulations of a one-dimensional model with a rectangular-well pair potential. The simulations support the relevance of the cell model to characterize basic properties of gravitational systems.     

Ensemble inequivalence in random graphs

We present a complete analytical solution of a system of Potts spins on a random k-regular graph in both the canonical and microcanonical ensembles, using the Large Deviation Cavity Method (LDCM). The solution is shown to be composed of three different branches, resulting in a non-concave entropy function. The analytical solution is confirmed with numerical Metropolis and Creutz simulations and our results clearly demonstrate the presence of a region with negative specific heat and, consequently, ensemble inequivalence between the canonical and microcanonical 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.     

Finite-size scaling in a microcanonical ensemble

The finite-size scaling technique is extended to a microcanonical ensemble. As an application, equilibrium magnetic properties of anL×L square lattice Ising model are computed using the microcanonical ensemble simulation technique of Creutz, and the results are analyzed using the microcanonical ensemble finite-size scaling. The computations were done on the multitransputer system of the Condensed Matter Theory Group at the University of Mainz.     

Bose gases in one-dimensional harmonic trap

Thermodynamic quantities, occupation numbers and their fluctuations of a one-dimensional Bose gas confined by a harmonic potential are studied using different ensemble approaches. Combining number theory methods, a new approach is presented to calculate the occupation numbers of different energy levels in microcanonical ensemble. The visible difference of the ground state occupation number in grand-canonical ensemble and microcanonical ensemble is found to decrease by power law as the number of particles increases.     

Pressure effects on diffusion in liquid ammonia : A simulation study using a combination of isobaric-isothermal and microcanonical molecular dynamics

The effects of pressure on translational and rotational diffusion in liquid ammonia are investigated by means of molecular dynamics simulations. Calculations are done at two different temperatures and at many different pressures by using a two-part protocol involving molecular dynamics in isobaric-isothermal ensemble in the first part and in microcanonical ensemble in the second part. Our results are analyzed in terms of pressure-induced changes in structural properties such as packing and hydrogen bond properties. Also, the present results of liquid ammonia are compared with corresponding results for other hydrogen bonded liquids that were reported in recent years.      

Direct calculation of fluctuation formulae in the microcanonical ensemble

We present simple derivations of the classical microcanonical ensemble formulae for fluctuations which involve the kinetic energy and microscopic pressure function. The new derivations, which confirm earlier results of Lebowitz et al. [1] and Cheung [2], proceed in a direct way from basic microcanonical ensemble theory without recourse to fluctuation expressions of other ensemble theories. The method developed is applicable to shell ensembles in general.     

Constrained molecular dynamics in the isothermal-isobaric ensemble and its adaptation for adiabatic free energy dynamics

The implementation of holonomic constraints within measure-preserving integrators for molecular dynamics simulations in the isothermal-isobaric ensemble is considered. We review the basic methodology of generating measure-preserving integrators for the microcanonical, canonical, and isothermal-isobaric ensembles and proceed to show how the standard SHAKE and RATTLE algorithms must be modified for the isothermal-isobaric ensemble. Comparison is made between constrained and unconstrained simulations employing multiple time scale integration techniques. Finally, we describe a temperature accelerated version of the isothermal-isobaric molecular dynamics approach, in which the cell matrix is adiabatically decoupled from the particles and maintained at a high temperature as a means of exploring polymorphism in molecular crystals. We demonstrate that constraints can be easily adapted for this new approach and, again, we compare the performace of this temperature-accelerated scheme with and without bond constraints.     

Thermodynamics of one-dimensional nonlinear lattices

Analytic equations were obtained for the thermodynamic parameters of one-dimensional lattices of particles with the Toda and Morse interaction potentials in a canonical Gibbs ensemble. For the same systems, equations were derived for molecular dynamics simulations of thermodynamic processes. Stochastic differential equations were solved with simulating the thermostat by Langevin sources with random forced. Analytic equations for thermodynamic parameters (energy, temperature, and pressure) excellently coincided with molecular dynamics simulation results. The kinetics of system relaxation to the thermodynamic equilibrium state was analyzed. The advantages of simulating the physical properties of systems in a canonical compared with microcanonical ensemble were demonstrated.     

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.     

Classification of Phase Transitions and Ensemble Inequivalence, in Systems with Long Range Interactions

Systems with long range interactions in general are not additive, which can lead to an inequivalence of the microcanonical and canonical ensembles. The microcanonical ensemble may show richer behavior than the canonical one, including negative specific heats and other non-common behaviors. We propose a classification of microcanonical phase transitions, of their link to canonical ones, and of the possible situations of ensemble inequivalence. We discuss previously observed phase transitions and inequivalence in self-gravitating, two-dimensional fluid dynamics and non-neutral plasmas. We note a number of generic situations that have not yet been observed in such systems.     

Microcanonical Finite-Size Scaling

In the microcanonical ensemble, suitably defined observables show nonanalyticities and power-law behavior even for finite systems. For these observables, a microcanonical finite-size scaling theory is established and combined with the experimentally observed power-law behavior. Scaling laws are obtained which relate exponents of the finite system and critical exponents of the infinite system to the system-size dependence of the affiliated microcanonical observables.     

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.     

Why there is something rather than nothing: cosmological constant from summing over everything in lorentzian quantum gravity

The density matrix of the Universe for the microcanonical ensemble in quantum cosmology describes an equipartition in the physical phase space of the theory (sum over everything), but in terms of the observable spacetime geometry this ensemble is peaked about the set of recently obtained cosmological instantons limited to a bounded range of the cosmological constant. This suggests the mechanism of constraining the landscape of string vacua and a possible solution to the dark energy problem in the form of the quasiequilibrium decay of the microcanonical state of the Universe.     

Collective dynamics near a phase transition in confined fluids

We performed molecular dynamics simulations in the microcanonical ensemble (MEMD) for a "simple" fluid confined between two solid substrates. From the calculation of the intermediate scattering function F(k( parallel ),t) and through the memory function formalism, we extract material ( i.e. transport and thermodynamics) coefficients in the vicinity of the liquid-gas phase transition. Our results show that approaching the limit of stability ( i.e. the spinodal), the dynamics of the system changes markedly.     

Complete Equivalence of the Gibbs Ensembles for One-Dimensional Markov Systems

We show the equivalence of the Gibbs ensembles at the level of measures for one-dimensional Markov-Systems with arbitrary boundary conditions. That is, the limit of the microcanonical Gibbs ensemble is a Gibbs measure with an interaction depending on the microcanonical constraint. In fact the usual microcanonical condition is replaced by the sharper constraint that all type frequencies of neighboring spins (including the boundary spins) are fixed. When conditioning on a set of different frequencies of neighboring spins compatible with physical quantities like energy density we get the usual microcanonical ensemble. We show that the limit is a Gibbs measure for a nearest neighbor potential depending on the pair measure which maximizes the entropy on the given set of pair measures. For this we show the large deviation property of the pair empirical measure for arbitrary boundary conditions. We establish analogous results for finite range potentials.     

Canonical typicality

It is well known that a system weakly coupled to a heat bath is described by the canonical ensemble when the composite S + B is described by the microcanonical ensemble corresponding to a suitable energy shell. This is true for both classical distributions on the phase space and quantum density matrices. Here we show that a much stronger statement holds for quantum systems. Even if the state of the composite corresponds to a single wave function rather than a mixture, the reduced density matrix of the system is canonical, for the overwhelming majority of wave functions in the subspace corresponding to the energy interval encompassed by the microcanonical ensemble. This clarifies, expands, and justifies remarks made by Schr?dinger in 1952.     

Microcanonical ensemble study of a gas column under gravity

The study of a classical ideal gas column of finite height H in a uniform gravitational field g is made by the microcanonical ensemble at energy E. The primary functions of this ensemble, the phase volume and the density of states, are derived. Related statistical quantities, such as the entropy, the temperature and the heat capacity, are also reported. The equivalence in the thermodynamic limit between the calculated microcanonical expressions and those obtained from the canonical ensemble is shown numerically. The expression for the temperature is used to analyze the temperature change when the gas is permitted to expand into an evacuated region increasing the height of the column from H ₁ to H ₂. The microcanonical single-particle momentum and height distributions are also reported.