Status of the Fundamental Laws of Thermodynamics

We describe recent progress towards deriving the Fundamental Laws of thermodynamics (the 0th, 1st, and 2nd Law) from nonequilibrium quantum statistical mechanics in simple, yet physically relevant models. Along the way, we clarify some basic thermodynamic notions and discuss various reversible and irreversible thermodynamic processes from the point of view of quantum statistical mechanics.     

Multiscale Thermodynamics

Multiscale thermodynamics is a theory of the relations among the levels of investigation of complex systems. It includes the classical equilibrium thermodynamics as a special case, but it is applicable to both static and time evolving processes in externally and internally driven macroscopic systems that are far from equilibrium and are investigated at the microscopic, mesoscopic, and macroscopic levels. In this paper we formulate multiscale thermodynamics, explain its origin, and illustrate it in mesoscopic dynamics that combines levels.     

Discovering Noncritical Organization: Statistical Mechanical,Information Theoretic,and Computational Views of Patterns in One-Dimensional Spin Systems

We compare and contrast three different, but complementary views of “structure” and “pattern” in spatial processes. For definiteness and analytical clarity, we apply all three approaches to the simplest class of spatial processes: one-dimensional Ising spin systems with finite-range interactions. These noncritical systems are well-suited for this study since the change in structure as a function of system parameters is more subtle than that found in critical systems where, at a phase transition, many observables diverge, thereby making the detection of change in structure obvious. This survey demonstrates that the measures of pattern from information theory and computational mechanics differ from known thermodynamic and statistical mechanical functions. Moreover, they capture important structural features that are otherwise missed. In particular, a type of mutual information called the excess entropy—an information theoretic measure of memory—serves to detect ordered, low entropy density patterns. It is superior in several respects to other functions used to probe structure, such as magnetization and structure factors. ϵ-Machines—the main objects of computational mechanics—are seen to be the most direct approach to revealing the (group and semigroup) symmetries possessed by the spatial patterns and to estimating the minimum amount of memory required to reproduce the configuration ensemble, a quantity known as the statistical complexity. Finally, we argue that the information theoretic and computational mechanical analyses of spatial patterns capture the intrinsic computational capabilities embedded in spin systems—how they store, transmit, and manipulate configurational information to produce spatial structure.     

Thermodynamics for Coulomb systems: A problem at vanishing particle densities

In this paper I combine techniques recently developed by Charles Fefferman with the well-known methods of Joel Lebowitz and Elliott Lieb to resolve some technical problems left unsettled by Lebowitz and Lieb's fundamental 1972 paper The constitution of matter: Existence of thermodynamics for systems composed of electrons and nuclei.     

Thermodynamics of rotating self-gravitating systems

We investigate the statistical equilibrium properties of a system of classical particles interacting via Newtonian gravity, enclosed in a three-dimensional spherical volume. Within a mean-field approximation, we derive an equation for the density profiles maximizing the microcanonical entropy and solve it numerically. At low angular momenta, i.e. for a slowly rotating system, the well-known gravitational collapse “transition” is recovered. At higher angular momenta, instead, rotational symmetry can spontaneously break down giving rise to more complex equilibrium configurations, such as double-clusters (“double stars”). We analyze the thermodynamics of the system and the stability of the different equilibrium configurations against rotational symmetry breaking, and provide the global phase diagram. Received 8 July 2002 Published online 15 October 2002 RID="a" ID="a"e-mail: demartino@hmi.de     

Hidden Symmetries for Thermodynamics and Emergence of Relativity

Erik Verlinde recently proposed an idea about the thermodynamic origin of gravity. Though this is a beautiful idea, which may resolve many long standing problems in the theories of gravity, it also raises many other problems. In this article I will comment on some of the problems of Verlinde＇s proposal with special emphasis on the thermodynamical origin of the principle of relativity. It is found that there is a large group of hidden symmetries of thermodynamics, which contains the Poincare group of the spacetime for which space is emergent. This explains the thermodynamic origin of the principle of relativity.     

q-Gaussian approximants mimic non-extensive statistical-mechanical expectation for many-body probabilistic model with long-range correlations

We study a strictly scale-invariant probabilistic N-body model with symmetric, uniform, identically distributed random variables. Correlations are induced through a transformation of a multivariate Gaussian distribution with covariance matrix decaying out from the unit diagonal, as ρ/r ^α for r =1, 2, ..., N-1, where r indicates displacement from the diagonal and where 0 ⩽ ρ ⩽ 1 and α ⩾ 0. We show numerically that the sum of the N dependent random variables is well modeled by a compact support q-Gaussian distribution. In the particular case of α = 0 we obtain q = (1-5/3 ρ) / (1- ρ), a result validated analytically in a recent paper by Hilhorst and Schehr. Our present results with these q-Gaussian approximants precisely mimic the behavior expected in the frame of non-extensive statistical mechanics. The fact that the N → ∞ limiting distributions are not exactly, but only approximately, q-Gaussians suggests that the present system is not exactly, but only approximately, q-independent in the sense of the q-generalized central limit theorem of Umarov, Steinberg and Tsallis. Short range interaction (α > 1) and long range interactions (α < 1) are discussed. Fitted parameters are obtained via a Method of Moments approach. Simple mechanisms which lead to the production of q-Gaussians, such as mixing, are discussed.      

Hidden Symmetries for Thermodynamics and Emergence of Relativity

Erik Verlinde recently proposed an idea about the thermodynamic origin ofgravity. Though this is a beautiful idea, which may resolve many longstanding problems in the theories of gravity, it also raises many otherproblems. In this article I will comment on some of the problems ofVerlinde's proposal with special emphasis on the thermodynamical originof the principle of relativity. It is found that there is a large group of hiddensymmetries of thermodynamics, which contains the Poincare group of thespacetime for which space is emergent. This explains the thermodynamicorigin of the principle of relativity.     

Thermodynamics and surface properties of liquid Cu–B alloys

The study of the thermodynamic and the surface properties of liquid Cu–B alloys can help better understanding of a complex interfacial chemistry related to liquid Cu–brazes in contact with boride substrates. Despite a simplicity of the Cu–B phase diagram, only a few thermodynamic data are available in the literature, while in the case of the surface properties a complete lack of data is evident. The quasi-chemical approximation (QCA) for the regular solution has been applied to describe the mixing behaviour of liquid Cu–B alloys in terms of their thermodynamic and surface properties as well as the microscopic functions. In view of joining processes related to liquid Cu–brazes/solid boride systems a particular attention is paid to the surface properties of the Cu-rich part of the system and the calculated values are substantiated by the new surface tension experimental data of liquid Cu and Cu–10 at.% B alloy. The tests have been performed by the sessile-drop method under the same experimental conditions. Considering the experimental uncertainties, the effect of oxygen on the surface tension of liquid Cu and Cu–10 at.% B alloy has been analysed by simple model that combines the physical property data included in Butler’s equation with the oxygen solubility data and it gives the same results as Belton’s adsorption equation.     

Thermodynamics of the Apparent Horizon in FRW Universe with Massive Gravity

Applying Clausius relation with energy-supply defined by the unified first law of thermodynamics formalism to the apparent horizon of a massive gravity model in cosmology proposed lately, the corrected entropic formula of the apparent horizon is obtained with the help of the modified Friedmann equations. This entropy-area relation, together with the identified Misner-Sharp internal energy, verifies the first law of thermodynamics for the apparent horizon with a volume change term for consistency. On the other hand, by means of the corrected entropy-area formula and the Clausius relation δQ=TdS, where the heat flow δQ is the energy-supply of pure matter projecting on the vector ξ tangent to the apparent horizon and should be looked on as the amount of energy crossing the apparent horizon during the time interval dt and the temperature of the apparent horizon for energy crossing during the same interval is 1/(2πA), the modified Friedmann equations governing the dynamical evolution of the universe are reproduced with the known energy density and pressure of massive graviton. The integration constant is found to correspond to a cosmological term which could be absorbed into the energy density of matter. Having established the correspondence of massive cosmology with the unified first law of thermodynamics on the apparent horizon, the validity of the generalized second law of thermodynamics is also discussed by assuming the thermal equilibrium between the apparent horizon and the matter field bounded by the apparent horizon. It is found that, in the limit Hc→0, which recovers the Minkowski reference metric solution in the flat case, the generalized second law of thermodynamics holds if α3+4α40. Without this condition, even for the simplest model of dRGT massive cosmology with α3 =α4 =0, the generalized second law of thermodynamics could be violated.     

A note on limitations of standard thermodynamics

Recently, as a common foundation of various branches in science, thermodynamics is getting fresh notice. One of the reasons are long‐range forces that may have far‐reaching consequences for the applicability of standard thermodynamics. In this paper we trace these consequences in connection with gravity, particle physics, condensed matter physics, and plasma physics. We point on scenarios (like hot plasmas of elementary particles in the early universe) where usually the applicability of standard thermodynamics is not even questioned. Therefore we wish to attract the reader's attention to such cases and mention some first steps towards non‐standard thermodynamics. It is, however, too early to propose final solutions at the present stage. We wish to provoke thoughts about the “old” thermodynamics from a modern perspective.     

Duality and Hidden Symmetries in Interacting Particle Systems

In the context of Markov processes, both in discrete and continuous setting, we show a general relation between duality functions and symmetries of the generator. If the generator can be written in the form of a Hamiltonian of a quantum spin system, then the “hidden” symmetries are easily derived. We illustrate our approach in processes of symmetric exclusion type, in which the symmetry is of SU(2) type, as well as for the Kipnis-Marchioro-Presutti (KMP) model for which we unveil its SU(1,1) symmetry. The KMP model is in turn an instantaneous thermalization limit of the energy process associated to a large family of models of interacting diffusions, which we call Brownian energy process (BEP) and which all possess the SU(1,1) symmetry. We treat in details the case where the system is in contact with reservoirs and the dual process becomes absorbing.     

Thermodynamics of the Apparent Horizon in FRW Universe with Massive Gravity

Applying Clausius relation with energy-supply defined by the unified first law of thermodynamics formalism to the apparent horizon of a massive gravity model in cosmology proposed lately, the corrected entropic formula of the apparent horizon is obtained with the help of the modified Friedmann equations. This entropy-area relation, together with the identified Misner-Sharp internal energy, verifies the first law of thermodynamics for the apparent horizon with a volume change term for consistency. On the other hand, by means of the corrected entropy-area formula and the Clausius relation δQ=T dS, where the heat flow δQ is the energy-supply of pure matter projecting on the vector ζ tangent to the apparent horizon and should be looked on as the amount of energy crossing the apparent horizon during the time interval dt and the temperature of the apparent horizon for energy crossing during the same interval is 1/2πrA, the modified Friedmann equations governing the dynamical evolution of the universe are reproduced with the known energy density and pressure of massive graviton. The integration constant is found to correspond to a cosmological term which could be absorbed into the energy density of matter. Having established the correspondence of massive cosmology with the unified first law of thermodynamics on the apparent horizon, the validity of the generalized second law of thermodynamics is also discussed by assuming the thermal equilibrium between the apparent horizon and the matter field bounded by the apparent horizon. It is found that, in the limit H_c→0, which recovers the Minkowski reference metric solution in the flat case, the generalized second law of thermodynamics holds if α₃+4α₄<0. Without this condition, even for the simplest model of dRGT massive cosmology with α₃=α₄=0, the generalized second law of thermodynamics could be violated.     

The third law of thermodynamics and the degeneracy of the ground state for lattice systems

The third law of thermodynamics, in the sense that the entropy per unit volume goes to zero as the temperature goes to zero, is investigated within the framework of statistical mechanics for quantum and classical lattice models. We present two main results: (i) For all models the question of whether the third law is satisfied can be decided completely in terms of ground-state degeneracies alone, provided these are computed for all possible boundary conditions. In principle, there is no need to investigate possible entropy contributions from low-lying excited states, (ii) The third law is shown to hold for ferromagnetic models by an analysis of the ground states.Dedicated to Pierre Résibois. Work supported in part by NSF grant PHY-7825390 A01.     

D-Dimensional Dirac Fermions BEC-BCS Crossover Thermodynamics

An effective relativistic continuum massive Proca Lagrangian action is used to account for the Lorentz vector condensation effects on the equation of state of the strongly interacting fermions system. The interior quantum fluctuation effects are incorporated as an external field approximation indirectly through a fictive generalized Thomson Problem counterterm background. The general analytical formulas for the d-dimensional thermodynamics are given near the unitary limit region. In the non-relativistic limit for d = 3, the universal dimensionless coefficient ξ = 4/9 and energy gap △/εf = 5/ 18 are reasonably consistent with the existing theoretical and experimental results. In the unitary limit for d = 2 and T = 0, the universal coefficient can even approach the extreme occasion ξ = 0 corresponding to the infinite effective fermion mass m* = ∞, which can be mapped to the strongly coupled two-dimensional electrons and is quite similar to the three-dimensional Bose-Einstein condensation of ideal boson gas. Instead, for d = 1, the universal coefficient ξ is negative, implying the non-existence of phase transition from superfluidity to normal state. The solutions manifest the quantum Ising universal class characteristic of the strongly coupled unitary fermions gas.     

Nonequilibrium Thermodynamics in Biochemical Systems and Its Application

Living systems are open systems, where the laws of nonequilibrium thermodynamics play the important role. Therefore, studying living systems from a nonequilibrium thermodynamic aspect is interesting and useful. In this review, we briefly introduce the history and current development of nonequilibrium thermodynamics, especially that in biochemical systems. We first introduce historically how people realized the importance to study biological systems in the thermodynamic point of view. We then introduce the development of stochastic thermodynamics, especially three landmarks: Jarzynski equality, Crooks’ fluctuation theorem and thermodynamic uncertainty relation. We also summarize the current theoretical framework for stochastic thermodynamics in biochemical reaction networks, especially the thermodynamic concepts and instruments at nonequilibrium steady state. Finally, we show two applications and research paradigms for thermodynamic study in biological systems.     

关于统计力学的基本原理

文章简要讨论有关统计力学基本原理的几个问题,包括正则系综理论、系综分布函数的支集、与热力学的对应、不可逆性及分布函数的时间演化。