Restricted Ensembles Research Articles

Bifurcation of solutions of Ornstein–Zernike equation in the gas–liquid coexistence region of simple fluids

One objective of this paper is to investigate bifurcation of solutions of Ornstein–Zernike equation in liquid state theory for the gas–liquid coexistence region of simple fluids. The analysis uses a discrete form of the Ornstein–Zernike equation in real space, together with a closure relation which provides nearly self consistent thermodynamic properties of fluids governed by interaction potentials like the Lennard-Jones potential. Accurate asymptotic forms of correlation functions are incorporated in the real space algorithm so as to mitigate the influence of cutoff length used in the discrete approximations. The global error reduction of this algorithm is similar to that of Simpson’s rule. It is found that there is no spinodal on the vapor side on a sub-critical isotherm. However, there is a density at which compressibility vanishes, but this lies on a nonphysical branch. There are fold bifurcation points on the vapor and liquid sides together with a ‘no-real-solution-region’ in between. This is followed by a region of negative compressibility extending up to the spinodal on the liquid side. Importantly, it is found that in regions where compressibility is non-positive, there are infinite number of solutions to OZE which violate an integral constraint that is needed for applications to thermodynamics. The emerging picture is somewhat similar to that in the case of the hypernetted-chain-closure. It is also found that complex solutions connect the physical solutions that exist outside the ‘no-real-solution-region’ as well as in region of negative compressibility. The second objective of the paper, in the light of bifurcation scenario, is to evolve an interpretation of the coupling-parameter expansion of correlation functions pertaining to the region of negative compressibility. It is shown that the expansion provides an accurate description of results of the restricted ensembles, implied in mean field theories and simulation methods. Bifurcation of singlet density to an in-homogeneous distribution at a spinodal is also established using a simple equation, which uses the direct correlation function. Thus the paper re-establishes the fact that restriction to a homogeneous singlet density is the root cause of all inconsistencies found in the gas–liquid coexistence region.

Statistical ensembles for phase coexistence states specified by noncommutative additive observables

A phase coexistence state cannot be specified uniquely by any intensive parameters, such as the temperature and the magnetic field, because they take the same values over all coexisting phases. It can be specified uniquely only by an appropriate set of additive observables. Hence, to analyze phase coexistence states the statistical ensembles that are specified by additive observables have been employed, such as the microcanonical and restricted ensembles. However, such ensembles are ill-defined or ill-behaved when some of the additive observables do not commute with each other. Here, we solve this fundamental problem by extending a generalized ensemble in such a way that it is applicable to phase coexistence states that are specified by noncommutative additive observables. We prove that this ensemble correctly gives the density matrix corresponding to phase coexistence states of general quantum systems as well as the thermodynamic functions. Furthermore, these ensembles are convenient for practical calculations because of their good analytic properties and useful formulas by which temperature and other intensive parameters are directly obtained from the expectation values of the additive observables. As a demonstration, we apply our formulation to a two-dimensional system whose phase coexistence states are specified by an additive observable (order parameter) that does not commute with the Hamiltonian.

Metastable states, quasi-stationary distributions and soft measures

We establish metastability in the sense of Lebowitz and Penrose under practical and simple hypotheses for Markov chains on a finite configuration space in some asymptotic regime. By comparing restricted ensembles and quasi-stationary measures, and introducing soft measures as an interpolation between the two, we prove an asymptotic exponential exit law and, on a generally different time scale, an asymptotic exponential transition law. By using potential-theoretic tools, and introducing “(κ,λ)-capacities”, we give sharp estimates on relaxation time, as well as mean exit time and transition time. We also establish local thermalization on shorter time scales.

ViennaRNA Package 2.0

BackgroundSecondary structure forms an important intermediate level of description of nucleic acids that encapsulates the dominating part of the folding energy, is often well conserved in evolution, and is routinely used as a basis to explain experimental findings. Based on carefully measured thermodynamic parameters, exact dynamic programming algorithms can be used to compute ground states, base pairing probabilities, as well as thermodynamic properties.ResultsThe ViennaRNA Package has been a widely used compilation of RNA secondary structure related computer programs for nearly two decades. Major changes in the structure of the standard energy model, the Turner 2004 parameters, the pervasive use of multi-core CPUs, and an increasing number of algorithmic variants prompted a major technical overhaul of both the underlying RNAlib and the interactive user programs. New features include an expanded repertoire of tools to assess RNA-RNA interactions and restricted ensembles of structures, additional output information such as centroid structures and maximum expected accuracy structures derived from base pairing probabilities, or z-scores for locally stable secondary structures, and support for input in fasta format. Updates were implemented without compromising the computational efficiency of the core algorithms and ensuring compatibility with earlier versions.ConclusionsThe ViennaRNA Package 2.0, supporting concurrent computations via OpenMP, can be downloaded from http://www.tbi.univie.ac.at/RNA.

Light scattering by morphologically complex objects and opposition effects (a review)

Over the last decade, considerable progress has been achieved in the theory of light scattering by morphologically complex objects, which extends the potential of correct interpretation of photometric and polarimetric observations. This especially concerns the backscattering domain, where the opposition effects in brightness and polarization are observed. Although the equations of radiative transfer and weak localization (coherent backscattering) are rigorously valid only for sparse media, the results of exact computer solutions of the Maxwell equations for a macroscopic volume filled with randomly positioned particles show that their application area can be wider. In particular, the observations can be correctly interpreted if the packing density of particles in the medium reaches 20–30%. The recently suggested approximate solution of the coherent backscattering problem allowed interesting effects in the spectra of Saturn’s satellites to be explained. In the densely packed media, the effects that are impossible in the sparse media and caused by the near-field contribution can be observed. To calculate the characteristics of radiation reflected by such a medium, it is not sufficient to solve the radiative transfer and weak localization equations, even if they are written in a form without the far-zone limitations. Nowadays, the influence of the interaction of particles in the near field can be analyzed only for the restricted ensembles of particles. It shows that the substantial increase of the packing density essentially changes the phase functions of intensity and polarization in the backscattering domain. This allows the packing density of particles in the medium and their absorbing properties to be estimated from the shape of the phase curves measured. However, the task of quantitative interpretation of the measurements of radiation reflected by a densely packed medium, in terms of sizes of particles, their refractive index, and packing density, still remains unsolved.

Coset Codes for Compound Multiple Access Channels With Common Information

Code construction is considered for arbitrary discrete memoryless compound multiple access channels (MACs) with common information. This class of channels includes MACs with/without common messages or with partially cooperating encoders. A construction method of code ensembles based on coset codes is proposed for these channels. Assuming joint maximum likelihood decoding, the performance of the proposed code ensemble is analyzed by deriving a lower bound on error exponents. A condition assuring that codes achieve the capacity region on average is given. It is seen that an elaborate combination of good linear codes gives capacity achieving codes for compound MACs with common messages or with partially cooperating encoders. The use of restricted ensembles with low-density parity check (LDPC) codes as component codes is also discussed. It is shown that a coset code ensemble based on nonbinary regular LDPC codes approaches the random coding exponent, and thus is capacity-achieving.

Some Universal Properties for Restricted Trace Gaussian Orthogonal, Unitary and Symplectic Ensembles

Consider fixed and bounded trace Gaussian orthogonal, unitary and symplectic ensembles, closely related to Gaussian ensembles without any constraint. For three restricted trace Gaussian ensembles, we prove universal limits of correlation functions at zero and at the edge of the spectrum edge. In addition, by using the universal result in the bulk for fixed trace Gaussian unitary ensemble, which has been obtained by G$\ddot{o}$tze and Gordin, we also prove universal limits of correlation functions for bounded trace Gaussian unitary ensemble.

Nonergodic activated kinetics in polar media

A theoretical formulation is developed for the activated kinetics when some subset of nuclear modes of the thermal bath is slower than the reaction and ergodicity of the thermal bath is not maintained. Nonergodic free energy profiles along the reaction coordinate are constructed by using restricted canonical ensembles with the phase space available to the system found by solving a self-consistent kinetic equation. The resulting activation barrier incorporates not only thermodynamic parameters but also dynamical information from the time autocorrelation function of the solute-solvent interaction energy. The theory is applied to the reactions of solvolysis and charge transfer in polar media.

Potts Models in the Continuum. Uniqueness and Exponential Decay in the Restricted Ensembles

In this paper we study a continuum version of the Potts model, where particles are points in ℝd, d≥2, with a spin which may take S≥3 possible values. Particles with different spins repel each other via a Kac pair potential of range γ −1, γ>0. In mean field, for any inverse temperature β there is a value of the chemical potential λ β at which S+1 distinct phases coexist. We introduce a restricted ensemble for each mean field pure phase which is defined so that the empirical particles densities are close to the mean field values. Then, in the spirit of the Dobrushin-Shlosman theory (Dobrushin and Shlosman in J. Stat. Phys. 46(5–6):983–1014, 1987), we prove that while the Dobrushin high-temperatures uniqueness condition does not hold, yet a finite size condition is verified for γ small enough which implies uniqueness and exponential decay of correlations. In a second paper (De Masi et al. in Coexistence of ordered and disordered phases in Potts models in the continuum, 2008), we will use such a result to implement the Pirogov-Sinai scheme proving coexistence of S+1 extremal DLR measures.

Extreme value statistics of eigenvalues of Gaussian random matrices

We compute exact asymptotic results for the probability of the occurrence of large deviations of the largest (smallest) eigenvalue of random matrices belonging to the Gaussian orthogonal, unitary, and symplectic ensembles. In particular, we show that the probability that all the eigenvalues of an (NxN) random matrix are positive (negative) decreases for large N as approximately exp [-beta theta(0)N2] where the Dyson index beta characterizes the ensemble and the exponent theta(0)=(ln 3)/4=0.274653... is universal. We compute the probability that the eigenvalues lie in the interval [zeta1,zeta2] which allows us to calculate the joint probability distribution of the minimum and the maximum eigenvalue. As a by-product, we also obtain exactly the average density of states in Gaussian ensembles whose eigenvalues are restricted to lie in the interval [zeta1,zeta2] , thus generalizing the celebrated Wigner semi-circle law to these restricted ensembles. It is found that the density of states generically exhibits an inverse square-root singularity at the location of the barriers. These results are confirmed by numerical simulations. Some of the results presented in detail here were announced in a previous paper [D. S. Dean and S. N. Majumdar, Phys. Rev. Lett. 97, 160201 (2006)].

Pico-canonical ensembles: a theoretical description of metastable states

We define restricted ensembles, called pico-canonical ensembles, for a statistical-mechanical description of the metastable and glassy phases. In this approach, time evolution is Markovian, with temperature dependent rates. Below a particular glass temperature, the system is strongly non-ergodic, and the phase space breaks up into a large number of mutually disconnected sectors. Averages are calculated over states within one such sector, and then averaged over sectors. As a soluble example, we calculate these explicitly for a one-dimensional lattice gas with nearest-neighbor couplings.

Microscopic description of hot nuclei: the SPA+RPA approach

We discuss the static path plus random phase approximation (SPA+RPA) to the partition function of warm finite nuclei. The method, derived from the auxiliary field path integral representation of the partition function, takes into account large amplitude statistical fluctuations around the mean field, and is able to provide an accurate evaluation of thermodynamics properties within finite configuration spaces. We present some recent improvements which include the treatment of repulsive terms in the interaction, the exact implementation in canonical and in restricted grand canonical ensembles with fixed number parity, and the evaluation of response and strength functions.

First order phase transitions in lattice and continuous systems: Extension of Pirogov-Sinai theory

We generalize the notion of “ground states” in the Pirogov-Sinai theory of first order phase transitions at low temperatures, applicable to lattice systems with a finite number of periodic ground states to that of “restricted ensembles” with equal free energies. A restricted ensemble is a Gibbs ensemble, i.e. equilibrium probability measure, on a restricted set of configurations in the phase space of the system. When a restricted ensemble contains only one configuration it coincides with a ground state. In the more general case the entropy is also important.An example of a system we can treat by our methods is theq-state Potts model where we prove that forq sufficiently large there exists a temperature at which the system coexists inq+1 phases;q-ordered phases are small modifications of theq perfectly ordered ground states and one disordered phase which is a modification of the restricted ensemble consisting of all “perfectly disordered” (neighboring sites must have different spins) configurations. The free energy thus consists entirely of energy in the firstq-restricted ensembles and of entropy in the last one.Our main motivation for this work is to develop a rigorous theory for phase transitions in continuum fluids in which there is no symmetry between the phases, e.g. the liquid-vapour phase transition. The present work goes a certain way in that direction.