Functional Integrals and Variational-Cumulant Expansion in sine-Gordon-Thirring Model

The free energy in 1D sine-Gordon-Thirring model with impurity coupling is studied by means of functional integrals and variational-cumulant expansion methods. Two variational parameters are introduced to evaluate free energy and statistical averages. It is shown that the non-perturbation method of functional integrals can be applied to strong-coupling range of fermion systems.     

Thermal Casimir effect in ideal metal rectangular boxes

The thermal Casimir effect in ideal metal rectangular boxes is considered using the method of zeta functional regularization. A renormalization procedure is suggested which provides the finite expression for the Casimir free energy in any restricted quantization volume. This expression satisfies the classical limit at high temperature and leads to zero thermal Casimir force for systems with infinite characteristic dimensions. In the case of two parallel ideal metal planes the results, as derived previously using thermal quantum field theory in Matsubara formulation and other methods, are reproduced starting from the expression obtained. It is shown that for rectangular boxes the temperature-dependent contribution to the electromagnetic Casimir force can be both positive and negative depending on side lengths. Numerical computations of the scalar and electromagnetic Casimir free energy and force are performed for cubes.     

Generalized lattice model of liquid state and its relation to Ginzburg–Landau theory

Basic principles of the generalized lattice model of multicomponent condensed systems are formulated. Short-range parts of interatomic interactions are taken into account by means of the geometric constraints method. Long-range parts of the interactions are taken into account in mean field approximation. The expression for Helmholtz free energy is obtained. A system of integral equations for the equilibrium distributions of components is derived. The asymptotic properties of its solutions are investigated. Moment expansion of interatomic interactions and localization of integral terms in free energy is obtained. A Ginzburg–Landau-like functional of free energy is derived.     

Equivalence of the Two Results for the Free Energy of the Chiral Potts Model

The free energy of the chiral Potts model has been obtained in two ways. The first used only the star-triangle relation, symmetries, and invariances, and led to a system of equations that implicitly define the free energy, and from which the critical behavior can be obtained The second used the functional relations derived by Bazhanov and Stroganov, solving them to obtain the free energy explicitly as a double integral. Here we obtain, for the first time, a direct verification that the two results are identical at all temperatures.     

Gibbs free energy and equilibrium states in the Si/Si oxide systems

In this paper, the equilibrium states in the Si/Si oxide systems formed as a result of the phase separation of nonstoichiometric silicon oxide films are studied. The expressions for the Gibbs free energy of Si oxide and Si/Si oxide systems are derived thermodynamically. The transformations of the Gibbs free energy in the amorphous Si/Si oxide and the crystalline Si/Si oxide systems with the change in the amount of separated silicon and the composition of the silicon oxide phase are analyzed. By minimizing the Gibbs free energy of these systems, the equilibrium stoichiometry indices of silicon oxide are calculated as functions of its initial stoichiometry and the temperature. The solubility limits of Si in SiO(2) in equilibrium with amorphous and crystalline Si are determined. The obtained results form the basis for the development of a complete thermodynamic theory of phase separation in nonstoichiometric silicon oxide films with the formation of Si nanoinclusions in the silicon oxide matrix.     

Reconstructing Free Energy Profiles from Nonequilibrium Relaxation Trajectories

Reconstructing free energy profiles is an important problem in bimolecular reactions, protein folding or allosteric conformational changes. Nonequilibrium trajectories are readily measured experimentally, but their statistical significance and relation to equilibrium system properties still call for rigorous methods of assessment and interpretation. Here we introduce methods to compute the equilibrium free energy profile of a given variable from a set of short nonequilibrium trajectories, obtained by externally driving a system out of equilibrium and subsequently observing its relaxation. This protocol is not suitable for the Jarzynski equality since the irreversible work on the system is instantaneous. Assuming that the variable of interest satisfies an overdamped Langevin equation, which is frequently used for modeling biomolecular processes, we show that the trajectories sample a nonequilibrium stationary distribution that can be calculated in closed form. This allows for the estimation of the free energy via an inversion procedure that is analogous to that used in equilibrium and bypasses more complicated path integral methods, which we derive for comparison. We generalize the inversion procedure to systems with a diffusion constant that depends on the reaction coordinate, as is the case in protein folding, as well as to protocols in which the trajectories are initiated at random points. Using only a statistical pool of tens of synthetic trajectories, we demonstrate the versatility of these methods by reconstructing double and multi-well potentials, as well as a proposed profile for the hydrophobic collapse of a protein.     

On the relationship between the density functional formalism and the potential distribution theory for nonuniform fluids

It is shown that the variational principle for the grand potential of a nonuniform fluid as a functional of the singlet density yields the potential distribution theory for the equilibrium density. We derive the explicit form that the functional takes for a system of hard rods, and propose an approximate one for hard spheres. Attractive interactions are also considered in mean-field approximation. In all cases the pair direct correlation function of the nonuniform system is obtained and the density gradient expansion of the free energy is investigated.     

Monte Carlo Methods for Rough Free Energy Landscapes: Population Annealing and Parallel Tempering

Parallel tempering and population annealing are both effective methods for simulating equilibrium systems with rough free energy landscapes. Parallel tempering, also known as replica exchange Monte Carlo, is a Markov chain Monte Carlo method while population annealing is a sequential Monte Carlo method. Both methods overcome the exponential slowing associated with high free energy barriers. The convergence properties and efficiencies of the two methods are compared. For large systems, population annealing is closer to equilibrium than parallel tempering for short simulations. However, with respect to the amount of computation, parallel tempering converges exponentially while population annealing converges only inversely. As a result, for sufficiently long simulations parallel tempering approaches equilibrium more quickly than population annealing.     

On the short range magnetic order of iron aboveT c

A derivation of the ordering part of the free energy functional based on an expansion about the free energy of a random CPA tight-binding paramagnetic effective medium is presented. Considering the dominant term of this functional, which is of Heisenberg form, the static magnetic correlation function is calculated within a spherical model approximation. For some parameters a behaviour characteristics for systems with tendency to form helicoidal ordered structure belowT _c is observed.     

Integrable boundary Boltzmann weights and surface free energy inversion relations of the chiral Potts model

The integrability of the chiral Potts model with boundaries is considered in this paper. The boundary star-triangle relation determining the boundary Boltzmann weights for the chiral Potts model is presented. By solving the boundary star-triangle relation the boundary Boltzmann weights are obtained. The fusion procedure is then applied to derive the functional relations of the transfer matrices of the model with boundaries. From these functional relations the inversion relations of the surface free energies are extracted when the system size is big enough. Surprisingly, the inversion relation of the local surface free energy is as simple as those of other non-chiral models, but it has still to be solved.     

Thermodynamic Free Energy Behavior of Diblock Copolymer Chains Confined Between Planar Surfaces Having End-Tethered Flexible Polymer Molecules

A molecular model for the free energy of a confined system of diblock copolymer chains within a 2D slit with the interior surfaces having end-tethered chains is presented, based on a combined lattice and scaling theory approach. The thermodynamics of a model system, based on a constrained minimization of free energy, is explored as a function of the intermolecular energy parameters for interaction between the segments of block copolymer chains, end-tethered chains, and the surfaces. The effects of chain length and the block length ratio are investigated over a wide range of values. The results obtained are qualitative in nature; however, the model can be implemented to real systems provided appropriate parameterization of the model parameters to real systems can be performed. The phase diagrams obtained here provide ways for designing thermodynamically stable systems within the physical parametric variable space.     

Functional Integrals and Free Energy in sine-Gordon-Thirring Model with Impurity Coupling

The free energy at low temperature in 1D sine-Gordon-Thirring model with impurity coupling is studied by means of functional integrals method. For massive free sine-Gordon-Thirring model, free energy is obtained from perturbation expansion of functional determinant. Moreover, the free energy of massive model is calculated by use of an auxiliary Bose field method.     

Nonlocal Free Energy of a Spatially Inhomogeneous Superconductor

The microscopic approach is developed for obtaining of the free energy of a superconductor based on direct calculation of the vacuum amplitude. The free energy functional of the spatially inhomogeneous superconductor in a magnetic field is obtained with help of the developed approach. The obtained functional is generalization of Ginzburg-Landau functionals for any temperature, for arbitrary spatial variations of the order parameter and for the nonlocality of a magnetic response and the order parameter. Moreover, the nonlocality of the magnetic response is the consequence of order parameter's nonlocality. The extremals of this functional are considered in the explicit form in the low- and high-temperature limit at the condition of slowness of spatial variations of the order parameter.     

The lamellar-disorder interface: one-dimensional modulated profiles

We study interfacial behavior of a lamellar (stripe) phase coexisting with a disordered phase. Systematic analytical expansions are obtained for the interfacial profile in the vicinity of a tricritical point. They are characterized by a wide interfacial region involving a large number of lamellae. Our analytical results apply to systems with one dimensional symmetry in true thermodynamical equilibrium and are of relevance to metastable interfaces between lamellar and disordered phases in two and three dimensions. In addition, good agreement is found with numerical minimization schemes of the full free energy functional having the same one dimensional symmetry. The interfacial energy for the lamellar to disordered transition is obtained in accord with mean field scaling laws of tricritical points. Received: 28 March 1997 / Revised: 6 February 1998 / Accepted: 16 February 1998     

Spectroscopic transitions supporting chemiluminescence in the reaction of calcium with hydrogen chloride

The main aim of this study was to show that chemiluminescence transitions of free radicals and molecules formed during the reaction are important for stability. After detection of certain geometrical structures that are valuable for the reaction, the most likely electrical and vibrational transitions in density functional theory were determined. Another factor that suppresses or promotes electronic transitions, as well as geometric position, is the vibrational energy levels of the molecular system. In experimental studies, vibrational energy distributions are worth examining while studying electron density or population. In these geometric regions, the quantum states where the infrared transitions take place were calculated through the energy eigenvalues equation. Thus, the potential energy surface obtained by density functional theory method was compared with a realistic potential energy surface and experimental values in the literature. The stability of the nascent calcium chloride molecule is determined by the position of the hydrogen atom separated from the chlorine atom rather than the energy of the calcium atom.     

Thermodynamic properties of solvated peptides from selective integrated tempering sampling with a new weighting factor estimation algorithm

Conformational sampling under rugged energy landscape is always a challenge in computer simulations. The recently developed integrated tempering sampling, together with its selective variant (SITS), emerges to be a powerful tool in exploring the free energy landscape or functional motions of various systems. The estimation of weighting factors constitutes a critical step in these methods and requires accurate calculation of partition function ratio between different thermodynamic states. In this work, we propose a new adaptive update algorithm to compute the weighting factors based on the weighted histogram analysis method (WHAM). The adaptive-WHAM algorithm with SITS is then applied to study the thermodynamic properties of several representative peptide systems solvated in an explicit water box. The performance of the new algorithm is validated in simulations of these solvated peptide systems. We anticipate more applications of this coupled optimisation and production algorithm to other complicated systems such as the biochemical reactions in solution.     

Variational principle for regular and random Ising models on the cactus tree or on the usual lattice in the “cactus approximation”

The distribution functions and the free energy are expressed in terms of the effective fields for the regular and random Ising models of an arbitrary spin S on the generalized cactus tree. The same expressions apply to systems on the usual lattice in the “cactus approximation” in the cluster variation method. For an ensemble of random Ising models of an arbitrary spin S on the generalized cactus tree, the equation for the probability distribution function of the effective fields is set up and the averaged free energy is expressed in terms of the probability distribution. The same expressions apply to the system on the usual lattice in the “cactus approximation”. We discuss the quantities on the usual lattice when the system or the ensemble of random systems has the translational symmetry. Variational properties of the free energy for a system and of the averaged free energy for an ensemble of random systems are noted. The “cactus approximations” are applicable to the Heisenberg model as well as to the Ising model of an arbitrary spin, and to ensembles of random systems of these models.     

Group structure analysis for classical lattice systems with constraints: II. Zeroes of the partition function and unicity of states

The Asano-Ruelle method is used to discuss the zeroes of the partition function of arbitrary lattice systems with constraints. The group structure associated with these systems yields necessary and sufficient conditions to build up the partition function by Asano contractions. For a large class of systems with constraints, uniqueness of the symmetric equilibrium state, as well as analyticity properties of the free energy and the correlation functions, is established at sufficiently low temperature. Explicit analyticity domains are obtained for several models with constraints. Some properties of power sets are derived.     

A variational approach to dense relativistic matter using functional techniques

The zero temperature ground state of an infinite system of baryons interacting with each other through the exchange of scalar and vector mesons is studied by means of a variational principle appropriate to relativistic systems. A trial wavefunctional is constructed which represents the fluctuation of the quantum fields about their mean values. The renormalized ground-state energy is subsequently calculated at a point where the vacuum is stable. Renormalization to all orders in the strong coupling constants is thereby obtained. A simple expression for the binding energy per particle with three free parameters is found. These parameters are fixed by fitting to the observed nucleon mass and to the values of the fermi momentum and binding energy of nuclear matter. A prediction for the binding energy and equation of state of nuclear and neutron matter is obtained for densities far away from the density of normal nuclei. Finally, a comparison is made with results obtained by other authors who have used classical-perturbative methods for the same system.