Asymptotics of Varadhan-type and the Gibbs variational principle

For a large class of quantum models of mean-field type the thermodynamic limit of the free energy density is proved to be given by the Gibbs variational principle. The latter is shown to be equivalent to a non-commutative version of Varadhan's asymptotic formula.On leave from the Mathematical Institute HAS, Budapest, HungaryOn leave from the Dublin Institute for Advanced Studies, Dublin, Ireland     

Thermodynamic limit for classical systems with Coulomb interactions in a constant external field

We introduce a new method for studying the thermodynamic limit for systems of particles with Coulomb interactions. The method is based on calculating the potential energy of the Coulomb interactions from the electric or magnetic fields in the system rather than from the energy of the individual particle — particle interactions. We are able to include the effects of a constant external field being imposed at the boundary of the system. The difficulties associated with Coulomb potentials being not even weakly tempered are overcome by imposing the boundary condition that at the boundary of the region containing the particles, the electric or magnetic field has normal component equal to that of the applied field. We prove that the thermodynamic free energy density exists and is independent of the sequence of regions used to define the limit. We introduce sequences of regions all of the same shape and show that for these sequences of regions the thermodynamic free energy density is independent of shape. Finally, we prove that the thermodynamic free energy is a convex function of the density of particles and of the applied field.     

Dissipation and large thermodynamic fluctuations

The results of recent work of Kipnis, Olla, and Varadhan on the dynamic large deviations from a hydrodynamic limit for some interacting particle models are formally extended to a general hydrodynamic situation, including non-equilibrium steady states, as a fluctuation-dissipation hypothesis. The basic conjecture is that the exponent of decay in the probability of a large thermodynamic fluctuation is given by the dissipation of the force required to produce the fluctuation. It is shown that this hypothesis leads to a nonlinear version of Onsager-Machlup fluctuation theory that had previously been proposed by Graham. A direct consequence of the theory is a dynamic variational principle for the most probable thermodynamic history subject to imposed constraints (Onsager's principle of least dissipation). Following Graham, the theory leads also to a generalized potential, analogous to an equilibrium free energy, for the nonequilibrium steady state and an associated static variational principle. Finally, a formulation of nonlinear fluctuating hydrodynamics is proposed in which the noise enters multiplicatively so as to reproduce the conjectured large-deviations theory on a formal analogy with the results of Freidlin and Wentzell for finite-dimensional systems.     

Microstructures in interpenetrating polymer networks

Prevalence of patterned microstructures in interpenetrating polymer networks is well documented experimentally. Thermodynamic theories explaining this feature nonetheless have not been forthcoming. These enmeshed structures carry elastic energy and elevate in the thermodynamic limit the free energy of mixing. Yet why is the deviation from a supposed macroscopic phase separation? This confounding question needs to be answered; and in this paper a thermodynamic explanation is offered. Crosslinking is shown to reduce the effective driving force for macrophase separation. Long-range free energy of deformation gives rise to sinks in the phase evolution, suppressing long-wavelength (hydrodynamic mode) composition fluctuations which usually implode during spinodal decompositions, prodding macrophase separations. Consequently, nonequilibrium metastable structures with small phase domains would evolve. This study highlights lineaments of pattern in physical systems: a competition between short- and long-range forces or a time evolution of nonconserved order parameters or both. A new free energy of mixing is formulated to elucidate the structural novelties.     

The thermodynamic limit for jellium

The thermodynamic limit of the free energy, energy, pressure, and entropy is established for a neutral system of charged particles interacting with a fixed, uniformly charged background (jellium).     

Equilibrium state and free energy of an infinite mode dicke maser model

For an infinite mode Dicke maser model, we show that the infimum of the free energy over a class of translation-invariant product states is attained for a quasi-free state. Furthermore, the thermodynamic limit of the free energy is proved to exist and equals the quasi-free solution.     

Investigation of magnetic field effect on surface and finite-site free energy in one-dimensional Ising model of nanosystems

We investigate a one-dimensional (1-D) Ising model for finite-site systems. The finite-site free energy and the surface free energy are calculated via the transfer matrix method. We show that, at high magnetic fields, the surface free energy has an asymptotic limit. The absolute surface energy increases when the value of f (the ratio of magnetic field to nearest-neighbor interactions) increases, and for f?≥?10 approaches a constant value. For the values of f?≥?0.2, the finite-site free energy also increases, but slowly. The thermodynamic limit in which physical properties approach the bulk value is also explored.     

Ising model in the high density limit

It is proved that the free energy per spin in the thermodynamic limit of an Ising model on a lattice with coordination numberz approaches the classical Curie-Weiss free energy in the limitz→∞. The infinite spacial dimension limit of nearest neighbour lattice models is a special case of this result.     

On a class of exactly soluble statistical mechanical models with nonpolynomial interactions

The approximating Hamiltonian method of N. N. Bogolubov, Jr. is generalized to models with nonpolynomial intensive-observable interactions. The original Hamiltonian is proved to be thermodynamically equivalent to one linear in the intensive-observable trial Hamiltonian. We show that the exact expression for the free energy density in the thermodynamic limit can be obtained from a min-max principle for the system with trial Hamiltonian.On leave of absence from Institute for Nuclear Research and Nuclear Energetics, Bulgarian Academy of Sciences, Sofia, Bulgaria.On leave of absence from Institute for Solid State Physics, Bulgarian Academy of Sciences, Sofia, Bulgaria.     

Life, hierarchy, and the thermodynamic machinery of planet Earth

Throughout Earth's history, life has increased greatly in abundance, complexity, and diversity. At the same time, it has substantially altered the Earth's environment, evolving some of its variables to states further and further away from thermodynamic equilibrium. For instance, concentrations in atmospheric oxygen have increased throughout Earth's history, resulting in an increased chemical disequilibrium in the atmosphere as well as an increased redox gradient between the atmosphere and the Earth's reducing crust. These trends seem to contradict the second law of thermodynamics, which states for isolated systems that gradients and free energy are dissipated over time, resulting in a state of thermodynamic equilibrium. This seeming contradiction is resolved by considering planet Earth as a coupled, hierarchical and evolving non-equilibrium thermodynamic system that has been substantially altered by the input of free energy generated by photosynthetic life. Here, I present this hierarchical thermodynamic theory of the Earth system. I first present simple considerations to show that thermodynamic variables are driven away from a state of thermodynamic equilibrium by the transfer of power from some other process and that the resulting state of disequilibrium reflects the past net work done on the variable. This is applied to the processes of planet Earth to characterize the generation and transfer of free energy and its dissipation, from radiative gradients to temperature and chemical potential gradients that result in chemical, kinetic, and potential free energy and associated dynamics of the climate system and geochemical cycles. The maximization of power transfer among the processes within this hierarchy yields thermodynamic efficiencies much lower than the Carnot efficiency of equilibrium thermodynamics and is closely related to the proposed principle of Maximum Entropy Production (MEP). The role of life is then discussed as a photochemical process that generates substantial amounts of chemical free energy which essentially skips the limitations and inefficiencies associated with the transfer of power within the thermodynamic hierarchy of the planet. This perspective allows us to view life as being the means to transform many aspects of planet Earth to states even further away from thermodynamic equilibrium than is possible by purely abiotic means. In this perspective pockets of low-entropy life emerge from the overall trend of the Earth system to increase the entropy of the universe at the fastest possible rate. The implications of the theory are discussed regarding fundamental deficiencies in Earth system modeling, applications of the theory to reconstructions of Earth system history, and regarding the role of human activity for the future of the planet.     

Thermodynamic anomalies in the presence of general linear dissipation: from the free particle to the harmonic oscillator

A free particle coupled to a heat bath can exhibit a number of thermodynamic anomalies like a negative specific heat, reentrant classicality or a nonmonotonic entropy. These low-temperature phenomena are expected to be modified at very low temperatures where finite-size effects associated with the discreteness of the energy spectrum become relevant. In this paper, we explore in which form the thermodynamic anomalies visible in the specific heat and the entropy of the free damped particle appear for a damped harmonic oscillator. Since the discreteness of the oscillator’s energy spectrum is fully accounted for, the results are valid for arbitrary temperatures. As expected, they are in agreement with the third law of thermodynamics and indicate how the thermodynamic anomalies of the free damped particle can be reconciled with the third law. Particular attention is paid to the transition from the harmonic oscillator to the free particle when the limit of the oscillator frequency to zero is taken.     

Darwinian demons, evolutionary complexity, and information maximization

Natural selection is shown to be an extended instance of a Maxwell's demon device. A demonic selection principle is introduced that states that organisms cannot exceed the complexity of their selective environment. Thermodynamic constraints on error repair impose a fundamental limit to the rate that information can be transferred from the environment (via the selective demon) to the genome. Evolved mechanisms of learning and inference can overcome this limitation, but remain subject to the same fundamental constraint, such that plastic behaviors cannot exceed the complexity of reward signals. A natural measure of evolutionary complexity is provided by mutual information, and niche construction activity--the organismal contribution to the construction of selection pressures--might in principle lead to its increase, bounded by thermodynamic free energy required for error correction.     

The approximating Hamiltonian method for an infinite-mode Dicke maser model withA 2-term

A new Dicke-type maser model is proposed. In the thermodynamic limit it involves infinitly many modes and anA ²-term. The approximating Hamiltonian method (AHM) is shown to be valid for the exact calculation of the free energy per particle and some thermodynamic averages for this model in the thermodynamic limit. In the rotatingwave approximation the superradiant phase transition persists at the same temperature as in the model withoutA ²-term.     

Survey of segregation alteration of hydrogen-helium mixtures via structure factor

In this study, thermodynamic instabilities in hydrogen-helium fluid mixture have been analyzed. These kinds of investigations are inevitable for indicating hydrodynamic transitions in Hydrogen-Helium fluid mixture. Therefore, first we have derived equation of state of mixture via Barker-Henderson statistical perturbation theory. Moreover, we have used Yiping radial distribution function in calculating perturbed terms. Via equation of state, we have calculated excess Gibbs free energy and the Gibbs free energy in the long wavelength limit. By means of this energy in hand we could estimate degree of hetero-coordination and segregations of this mixture which is a measure for defining thermodynamic instabilities. At last, these measurements have made us capable of anticipating thermodynamic instabilities and coordination of mixture in different concentrations.     

Near-equilibrium measurements of nonequilibrium free energy

A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a nonequilibrium ensemble is that it is larger than that of the same system at equilibrium. Herein, we derive a formally exact expression for the probability distribution of a driven system, which involves path ensemble averages of the work over trajectories of the time-reversed system. From this we find a simple near-equilibrium approximation for the free energy in terms of an excess mean time-reversed work, which can be experimentally measured on real systems. With analysis and computer simulation, we demonstrate the accuracy of our approximations for several simple models.     

Rigorous Results for Hierarchical Models of Structural Glasses

We consider two non-mean-field models of structural glasses built on a hierarchical lattice. First, we consider a hierarchical version of the random energy model, and we prove the existence of the thermodynamic limit and self-averaging of the free energy. Furthermore, we prove that the infinite-volume entropy is positive in a high-temperature region bounded from below, thus providing an upper bound on the Kauzmann critical temperature. In addition, we show how to improve this bound by leveraging the hierarchical structure of the model. Finally, we introduce a hierarchical version of the \(p\) -spin model of a structural glass, and we prove the existence of the thermodynamic limit and self-averaging of the free energy.     

Path integral approach to polaron mass and radius at finite temperatures

Polaron effective mass and radius at finite temperatures are defined and exact path integral representations are given for them. Feynman's representation for the effective mass is obtained in the limit of zero temperature. Calculations are made in the framework of the variational principle for the free energy by using as trial functional the one corresponding to a simplified, exactly solvable model of electron-phonon interaction proposed by Bogolubov. Effective mass and radius dependence on temperature and coupling strength are discussed for some ranges of values of these parameters. Comparison with the experimental dependence of polaron cyclotron mass on temperature shows a reasonable agreement.     

Statistical mechanics of quasi-one-dimensional systems

A definition of a quasi-one-dimensional system as a generalized Cayley or Husimi tree with a nonzero surface to bulk ratio in the thermodynamic limit is given. Sufficient conditions for the existence of the thermodynamic limit of the free energy for such a system are derived and a thorough discussion of the thermodynamic limit properties of the one-particle distribution functions is given. These results are made more precise for the case of systems with Hamiltonians which are invariant under a special type of measure-preserving group of transformations, in particular for the d-dimensional rotation group. For this latter case, the phase transitions which can occur in quasi-one-dimensional systems upon application of small external fields are studied in some detail. A number of completely solved examples is given to illustrate the general theory. These include the classical Heisenberg model on a Cayley tree and generalizations thereof.