On the Helmholtz Potential Metric: The Isotherm Length-Work Theorem

In this paper we introduce the Isotherm Length-Work theorem using the Helmholtz potential metric and the virial expansion of pressure in inverse power of molar volume. The theorem tells us what length of a thermodynamical system described by equation of state through virial expansion along isotherms actually is with such a metric. We also give explicit solutions for thermodynamic length along isotherms in the case of first, second and third order expansion     

Contact symmetries and Hamiltonian thermodynamics

It has been shown that contact geometry is the proper framework underlying classical thermodynamics and that thermodynamic fluctuations are captured by an additional metric structure related to Fisher’s Information Matrix. In this work we analyse several unaddressed aspects about the application of contact and metric geometry to thermodynamics. We consider here the Thermodynamic Phase Space and start by investigating the role of gauge transformations and Legendre symmetries for metric contact manifolds and their significance in thermodynamics. Then we present a novel mathematical characterization of first order phase transitions as equilibrium processes on the Thermodynamic Phase Space for which the Legendre symmetry is broken. Moreover, we use contact Hamiltonian dynamics to represent thermodynamic processes in a way that resembles the classical Hamiltonian formulation of conservative mechanics and we show that the relevant Hamiltonian coincides with the irreversible entropy production along thermodynamic processes. Therefore, we use such property to give a geometric definition of thermodynamically admissible fluctuations according to the Second Law of thermodynamics. Finally, we show that the length of a curve describing a thermodynamic process measures its entropy production.     

Configurations and observables in an Ising model with heat flow

We study a two dimensional Ising model between thermostats at different temperatures. By applying the recently introduced KQ dynamics, we show that the system reaches a steady state with coexisting phases transversal to the heat flow. The relevance of such complex states on thermodynamic or geometrical observables is investigated. In particular, we study energy, magnetization and metric properties of interfaces and clusters which, in principle, are sensitive to local features of configurations. With respect to equilibrium states, the presence of the heat flow amplifies the fluctuations of both thermodynamic and geometrical observables in a domain around the critical energy. The dependence of this phenomenon on various parameters (size, thermal gradient, interaction) is discussed also with reference to other possible diffusive models.     

Fluctuations When Driving Between Nonequilibrium Steady States

Maintained by environmental fluxes, biological systems are thermodynamic processes that operate far from equilibrium without detailed-balanced dynamics. Yet, they often exhibit well defined nonequilibrium steady states (NESSs). More importantly, critical thermodynamic functionality arises directly from transitions among their NESSs, driven by environmental switching. Here, we identify the constraints on excess heat and dissipated work necessary to control a system that is kept far from equilibrium by background, uncontrolled “housekeeping” forces. We do this by extending the Crooks fluctuation theorem to transitions among NESSs, without invoking an unphysical dual dynamics. This and corresponding integral fluctuation theorems determine how much work must be expended when controlling systems maintained far from equilibrium. This generalizes thermodynamic feedback control theory, showing that Maxwellian Demons can leverage mesoscopic-state information to take advantage of the excess energetics in NESS transitions. We also generalize an approach recently used to determine the work dissipated when driving between functionally relevant configurations of an active energy-consuming complex system. Altogether, these results highlight universal thermodynamic laws that apply to the accessible degrees of freedom within the effective dynamic at any emergent level of hierarchical organization. By way of illustration, we analyze a voltage-gated sodium ion channel whose molecular conformational dynamics play a critical functional role in propagating action potentials in mammalian neuronal membranes.     

The Second Law of Thermodynamics at the Microscopic Scale

In quantum statistical mechanics, equilibrium states have been shown to be the typical states for a system that is entangled with its environment, suggesting a possible identification between thermodynamic and von Neumann entropies. In this paper, we investigate how the relaxation toward equilibrium is made possible through interactions that do not lead to significant exchange of energy, and argue for the validity of the second law of thermodynamics at the microscopic scale.     

Lattice Boltzmann model for combustion and detonation

In this paper we present a lattice Boltzmann model for combustion and detonation. In this model the fluid behavior is described by a finite-difference lattice Boltzmann model by Gan et al. [Physica A, 2008, 387: 1721]. The chemical reaction is described by the Lee-Tarver model [Phys. Fluids, 1980, 23: 2362]. The reaction heat is naturally coupled with the flow behavior. Due to the separation of time scales in the chemical and thermodynamic processes, a key technique for a successful simulation is to use the operator-splitting scheme. The new model is verified and validated by well-known benchmark tests. As a specific application of the new model, we studied the simple steady detonation phenomenon. To show the merit of LB model over the traditional ones, we focus on the reaction zone to study the non-equilibrium effects. It is interesting to find that, at the von Neumann peak, the system is nearly in its thermodynamic equilibrium. At the two sides of the von Neumann peak, the system deviates from its equilibrium in opposite directions. In the front of von Neumann peak, due to the strong compression from the reaction product behind the von Neumann peak, the system experiences a sudden deviation from thermodynamic equilibrium. Behind the von Neumann peak, the release of chemical energy results in thermal expansion of the matter within the reaction zone, which drives the system to deviate the thermodynamic equilibrium in the opposite direction. From the deviation from thermodynamic equilibrium, Δ _m *, defined in this paper, one can understand more on the macroscopic effects of the system due to the deviation from its thermodynamic equilibrium.     

The Approach Towards Equilibrium in a Reversible Ising Dynamics Model: An Information-Theoretic Analysis Based on an Exact Solution

We study the approach towards equilibrium in a dynamic Ising model, the Q2R cellular automaton, with microscopic reversibility and conserved energy for an infinite one-dimensional system. Starting from a low-entropy state with positive magnetisation, we investigate how the system approaches equilibrium characteristics given by statistical mechanics. We show that the magnetisation converges to zero exponentially. The reversibility of the dynamics implies that the entropy density of the microstates is conserved in the time evolution. Still, it appears as if equilibrium, with a higher entropy density is approached. In order to understand this process, we solve the dynamics by formally proving how the information-theoretic characteristics of the microstates develop over time. With this approach we can show that an estimate of the entropy density based on finite length statistics within microstates converges to the equilibrium entropy density. The process behind this apparent entropy increase is a dissipation of correlation information over increasing distances. It is shown that the average information-theoretic correlation length increases linearly in time, being equivalent to a corresponding increase in excess entropy.     

Representation invariant Geometrothermodynamics: Applications to ordinary thermodynamic systems

In this work we employ a recently devised metric within the Geometrothermodynamics program to study ordinary thermodynamic systems. The new feature of this metric is that, in addition to Legendre symmetry, it exhibits invariance under a change of representation. This metric was derived in a previous work by the authors while addressing the problem of the conformal structure of the thermodynamic metrics for different representations. Here, we present a thorough analysis for the ideal gas, the van der Waals fluid, the one dimensional Ising model and some other systems of cosmological interest.     

Variational Principle in the Theory of Partial Distribution Functions

We have constructed thermodynamically consistent theory of correlations in a classical equilibrium system. The theory is based on a variational principle for thermodynamic potential, as functional of correlation functions. Both the thermodynamic potential and correlation functions are determined simultaneously from a uniform variation problem for this functional. We have offered also methods of consecutive approximations system construction for the solution of the obtained variational problem.     

Free energy from molecular dynamics with multiple constraints

In molecular dynamics simulations of reacting systems, the key step to determining the equilibrium constant and the reaction rate is the calculation of the free energy as a function of the reaction coordinate. Intuitively the derivative of the free energy is equal to the average force needed to constrain the reaction coordinate to a constant value, but the metric tensor effect of the constraint on the sampled phase space distribution complicates this relation. The appropriately corrected expression for the potential of mean constraint force method (PMCF) for systems in which only the reaction coordinate is constrained was published recently. Here we will consider the general case of a system with multiple constraints. This situation arises when both the reaction coordinate and the ‘hard’ coordinates are constrained, and also in systems with several reaction coordinates. The obvious advantage of this method over the established thermodynamic integration and free energy perturbation methods is that it avoids the cumbersome introduction of a full set of generalized coordinates complementing the constrained coordinates. Simulations of n-butane and n-pentane in vacuum illustrate the method.     

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.     

Fluctuations and stability of stationary non-equilibrium systems in detailed balance

A generalized thermodynamic potential for Markoffian systems with detailed balance and far from thermal equilibrium has been derived in a previous paper. It was shown that the principle of detailed balance is equivalent to a set of conditions fulfilled by this potential (“potential conditions”). The properties of this potential allow us to extend the validity of a number of thermodynamic concepts well known for systems in or near thermal equilibrium to stationary states far from thermal equilibrium. The concept of symmetry breaking phase transitions for these systems is introduced in analogy to thermal equilibrium systems by considering the dependence of the stationary probability density of the system on a set of externally controlled parameters {λ}. A functional of the time dependent probability density of the system is defined in close analogy to the Gibb's definition of entropy. This functional has the properties of a Ljapunov functional of the governing Fokker-Planck equation showing the stability of the stationary probability density. The Langevin equations connected with the Fokker-Planck equation are considered. It is shown that, by means of the potential conditions, generalized “thermodynamic” fluxes and forces may be defined in such a way that the smoothly varying part of the Langevin equations (kinetic equations) constitutes a linear relation between fluxes and forces. The matrix of coefficients is given by the diffusion matrix of the Fokker-Planck equation. The symmetry relations which hold for this matrix due to the potential conditions then lead to the Onsager-Casimir symmetry relations extended to systems with detailed balance near stationary states far from thermal equilibrium. Finally it is shown that under certain additional assumptions the generalized thermodynamic potential may be used as a Ljapunov function of the kinetic equations.     

Decrease in entropy as a result of measuring the time of escape from a potential well

The decrease in entropy when passing from an equilibrium thermodynamic system to a slightly nonequilibrium system is investigated. A quasi-equilibrium Boltzmann distribution is used to prove the conservation of free energy during this passage. Results are obtained for a Brownian particle in a potential well with a low escape probability. The escape is interpreted as a measurement. It is shown that because of the measurement itself, the distribution function is narrower than that for a system undisturbed by measurement, i.e., an equilibrium system. In this case, the entropy difference between the equilibrium and measurement-disturbed systems is equal to the amount of information entered into the system.     

Numerical simulation of stochastic motion of vortex loops under action of random force. Evidence of the thermodynamic equilibrium state

Numerical simulation of stochastic dynamics of vortex filaments under action of random (Langevin) force is fulfilled. Calculations are performed on base of the full Biot-Savart law for different intensities of the Langevin force. A new algorithm, which is based on consideration of crossing lines, is used for vortex reconnection procedure. After some transient period the vortex tangle develops into the stationary state characterizing by the developed fluctuations of various physical quantities, such as total length, energy etc. We tested this state to learn whether or not it the thermodynamic equilibrium is reached. With the use of a special treatment, so called method of weighted histograms, we process the distribution energy of the vortex system. The results obtained demonstrate that the thermodynamical equilibrium state with the temperature obtained from the fluctuation dissipation theorem is really reached.     

Monochromatic and mean radiative properties of astrophysical plasma mixtures in nonlocal thermodynamic equilibrium regime

Radiative-hydrodynamics and radiative transfer simulations of astrophysical plasmas require the determination of radiative properties. However, most of the plasma radiative properties are calculated assuming the plasma in coronal equilibrium or local thermodynamic equilibrium regimes that is often not the case for many scenarios. In this work, we present nonlocal thermodynamic equilibrium calculations of radiative opacities of Fe and S and of an astrophysical plasma mixture for temperatures larger than 100 eV. We also analyze the departure from local thermodynamic equilibrium simulations.     

强迫耗散系统的有序结构和系统的发展(Ⅰ)，最小熵产生原理和有序结构

一个系统的发展总是由不可逆热力过程和非线性动力过程所驱动.将大气动力学方程组同考虑了动能变化的Gibbs关系结合起来构建的熵平衡方程，才能更好地描述大气系统的不可逆热力过程和非线性动力过程.至今非平衡态热力学仅利用Onsager线性唯象关系证明了最小熵产生原理.利用新建立的熵平衡方程和大气动力学方程的性质证明，最小熵产生原理在热力学线性区和非线性区都是普遍成立的.且当热量输送平衡、水汽输送平衡和动量输送平衡时，系统达到不可逆过程最弱的最小熵产生热力学状态.当系统又是动力平衡且无平流时，这种最小熵产生态就是 关键词： 非线性热力学 熵产生 最小熵产生原理 有序结构     

Microscopic model approaches to fragmentation of nuclei and phase transitions in nuclear matter

The properties of excited nuclear matter and the quest for a phase transition which is expected to exist in this system are the subject of intensive investigations. High-energy nuclear collisions between finite nuclei which lead to matter fragmentation are used to investigate these properties. The present report covers effective work done on the subject over the two last decades. The analysis of experimental data is confronted with two major problems, the setting up of thermodynamic equilibrium in a time-dependent fragmentation process and the finite size of nuclei. The present status concerning the first point is presented. Simple classical models of disordered systems are derived starting with the generic bond percolation approach. These lattice and cellular equilibrium models, like percolation approaches, describe successfully experimental fragment multiplicity distributions. They also show the properties of systems which undergo a thermodynamic phase transition. Physical observables which are devised to show the existence and to fix the order of critical behaviour are presented. Applications to the models are shown. Thermodynamic properties of finite systems undergoing critical behaviour are advantageously described in the framework of the microcanonical ensemble. Applications to the designed models and to experimental data are presented and analysed. Perspectives of further developments of the field are suggested.     

How Does Pressure Fluctuate in Equilibrium?

We study fluctuations of pressure in equilibrium for classical particle systems. In equilibrium statistical mechanics, pressure for a microscopic state is defined by the derivative of a thermodynamic function or, more mechanically, through the momentum current. We show that although the two expectation values converge to the same equilibrium value in the thermodynamic limit, the variance of the mechanical pressure is in general greater than that of the pressure defined through the thermodynamic relation. We also present a condition for experimentally detecting the difference between them in an idealized measurement of momentum transfer.