Nonequilibrium thermodynamics in field theory: Transport coefficients

Transport coefficients are expressed by real time correlation functions of energy-momentum tensor in the linear response approximation. We establish field theoretical method to compute them in perturbation theory, which is demonstrated in λ?⁴ theory.     

Nonequilibrium thermodynamics and fluctuation relations for small systems

In this review, we give a retrospect of the recent progress in nonequilibrium statistical mechanics and thermodynamics in small dynamical systems. For systems with only a few number of particles, fluctuations and nonlinearity become significant and contribute to the nonequilibrium behaviors of the systems, hence the statistical properties and thermodynamics should be carefully studied. We review recent developments of this topic by starting from the Gallavotti–Cohen fluctuation theorem, and then to the Evans–Searles transient fluctuation theorem, Jarzynski free-energy equality, and the Crooks fluctuation relation. We also investigate the nonequilibrium free energy theorem for trajectories involving changes of the heat bath temperature and propose a generalized free-energy relation. It should be noticed that the non-Markovian property of the heat bath may lead to the violation of the free-energy relation.     

Nonequilibrium thermodynamics of lasing and bistable optical systems

A simple model of nonlinear optical systems exhibiting instability—such as in laser action and in bistable absorption—is presented that provides a prototype of nonequilibrium thermodynamics on a statistical basis. The adiabatic reduction of the atomic degrees of freedom in a revised Langevin treatment establishes a fully consistent framework in which the active electromagnetic field mode is in contact with two thermal reservoirs (the cavity and the atoms) as well as being acted upon by an external field. The results are summarized by the first and second laws,dE=W+Q _c +Q _A anddS Q_c/¯T_c+Q_A/¯T_A, with the statistical mechanical representations of the entities therein exhibiting the nature of the mode; i.e., (a) a heat-engine structure operating between two reservoirs of temperatures¯T _c > 0 and¯T _A < 0 for the laser, and (b) a nonlinear response against external work balanced by a single reservoir (¯ T _c = ¯T _A ) for the absorptive bistability.Originally presented at the Taniguchi Symposium, October 1979.⁴⁴     

Nonequilibrium dynamics and thermodynamics of a degenerate fermi gas across a feshbach resonance

We consider a two-species degenerate Fermi gas coupled by a diatomic Feshbach resonance. We show that the resulting superfluid can exhibit a form of coherent BEC-to-BCS oscillations in response to a nonadiabatic change in the system's parameters, such as, for example, a sudden shift in the position of the Feshbach resonance. In the narrow resonance limit, the resulting solitonlike collisionless dynamics can be calculated analytically. In equilibrium, the thermodynamics can be accurately computed across the full range of BCS-BEC crossover, with corrections controlled by the ratio of the resonance width to the Fermi energy.     

Nonequilibrium thermodynamics and the transport phenomena in magnetically confined plasmas

The neoclassical theory of transport in magnetically confined plasmas is reviewed. The emphasis is laid on a set of relationships existing among the banana transport coefficients. The surface-averaged entropy production in such plasmas is evaluated. It is shown that neoclassical effects emerge from the entropy production due to parallel transport processes. The Pfirsch-Schlüter effect can be clearly interpreted as due to spatial fluctuations of parallel fluxes on a magnetic surface: the corresponding entropy production is the measure of these fluctuations. The banana fluxes can be formulated in a quasithermodynamic form in which the average entropy production is a bilinear form in the parallel fluxes and the conjugate generalized stresses. A formulation as a quadratic form in the thermodynamic forces is also possible, but leads to anomalies, which are discussed in some detail.     

小系统的非平衡统计力学与随机热力学

热力学是一个古老的课题,古典热力学以宏观的具有大粒子数的系统为研究对象,自17世纪以来,科学家们构建了热力学的完备公理化体系。将热力学推广至小系统是近三十年来的研究前沿。文章介绍小系统的非平衡统计力学以及小系统的随机热力学。作为研究案例,利用时间依赖的谐振子势场控制单个粒子来构造随机热机的类卡诺循环,并发现该热机最大功率对应的效率等于1-,其中T_c和T_h分别对应于低温热库和高温热库的温度。     

Nonequilibrium thermodynamics and the optimal path to turbulence in shear flows

We determine the initial condition on the laminar-turbulent boundary closest to the laminar state using nonlinear optimization for plane Couette flow. Resorting to the general evolution criterion of nonequilibrium systems we optimize the route to the statistically steady turbulent state, i.e., the state characterized by the largest entropy production. This is the first time information from the fully turbulent state is included in the optimization procedure. We demonstrate that the optimal initial condition is localized in space for realistic flow domains.     

Nonequilibrium kinetics: Exact and approximate solutions

The relaxation of an internal state distribution in the presence of an excess of an inert gas is considered. The explicit time dependence of the nonequilibrium contributions to the transition rate coefficients is approximated using the Kapral-Hudson-Ross method. The resulting solution contains cross-correlation terms which do not appear when a single reaction is considered. It is shown that the first term of a perturbation expansion of an exact formal solution gives the Kapral-Hudson-Ross solution for short times, and the Chapman-Enskog solution at long times if there is a wide separation in time scales. The Kapral-Hudson-Ross, Chapman-Enskog, and exact solutions are compared for a two-state, hard-sphere model system.Based on a dissertation by S. Hudson, Massachusetts Institute of Technology, 1972.National Science Foundation predoctoral fellow, 1967–1971.     

Nonequilibrium thermodynamics of stochastic systems with odd and even variables

The total entropy production of stochastic systems can be divided into three quantities. The first corresponds to the excess heat, while the second two comprise the housekeeping heat. We denote these two components the transient and generalized housekeeping heat and we obtain an integral fluctuation theorem for the latter, valid for all Markovian stochastic dynamics. A previously reported formalism is obtained when the stationary probability distribution is symmetric for all variables that are odd under time reversal, which restricts consideration of directional variables such as velocity.     

Single molecule acid-base kinetics and thermodynamics

We report a method in which temperature dependent single-molecule fluorescence measurements are used to study the kinetics and thermodynamics of the acid-base interaction in films of photoresist polymer. We use the two distinct fluorescent prototropic forms of Coumarin 6 (C6-->C6+) to indicate the state of the acid-base system. Data are analyzed using a statistical model of the intensity probability distributions, yielding temperature dependent proton exchange rates, which is confirmed through agreement with a simple two-state Monte Carlo model. The temperature dependent rates are used to calculate the activation enthalpy for proton exchange.     

Nonequilibrium carrier and exciton kinetics in silicon and germanium crystals

Asymptotic small-parameter expansion is applied to the solutions for singularly perturbed systems in order to examine the kinetics of laser excitation for nonequilibrium carriers and excitons in silicon and germanium crystals, which incorporates nonequilibrium carrier recombination, linear recombination, and exciton formation and ionization. Asymptotic evaluations can be used that apply throughout the range in pulse length in order to provide indirect and rough estimates of the probabilities for various recombination and ionization processes.Baku State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 24–26, December, 1993.     

Equilibrium thermodynamics and thermodynamic processes in nonlinear systems

A general method for the calculation of thermodynamic quasi-equilibrium processes by molecular dynamics (MD) simulation in canonical ensemble is developed. The method is suitable for classical systems with arbitrary interaction potentials. Though this MD method does not allow to calculate directly partition function and entropy, it is possible to calculate necessary partial derivatives which enter into the expressions for the full derivatives dT/dV and d β/dV for adiabitic and isobaric processes. Namely the solutions of these ordinary differential equations define the corresponding thermodynamic processes. The adiabatic process for the 1D Toda lattice is analyzed in details. The usage of the Toda potential allows to perform all analytical calculus up to accurate answers and to compare numerical and analytical results. Exact analytical expressions for the thermodynamics of 1D lattices with few types of nearest neighbor interactions are obtained as a necessary interim solutions. MD-simulation of quasi equilibrium processes in canonical ensemble demands the achievement of thermodynamic equilibrium, thus the thermalization kinetics is briefly discussed.     

Nonequilibrium thermodynamics at the microscale: Work relations and the second law

For macroscopic systems, the second law of thermodynamics establishes an inequality between the amount of work performed on a system in contact with a thermal reservoir, and the change in its free energy. For microscopic systems, this result must be considered statistically, as fluctuations around average behavior become substantial. In recent years it has become recognized that these fluctuations satisfy a number of strong and unexpected relations, which remain valid even when the system is driven far from equilibrium. We discuss these relations, and consider what they reveal about the second law of thermodynamics and the nature of irreversibility at the microscale.     

Relation between thermodynamics and kinetics of glass-forming liquids

Vitrification of a supercooled liquid is often characterized by the hypothetical kinetic instability point, the Vogel-Fulcher temperature T0, and the thermodynamic one, the Kauzmann temperature T(K). The widely believed relation T0 congruent with T(K) is regarded as the supporting evidence of a direct connection between the thermodynamics and kinetics of glass-forming liquids. Here we demonstrate that T(K)/T(0) systematically increases from unity with a decrease in the fragility, contrary to the common belief. This systematic deviation may be explained by a synergistic effect between the weaker cooperativity and the stronger tendency of short-range ordering in stronger glass formers.     

Genetic alloy design based on thermodynamics and kinetics

A theory-guided computational approach for alloy design is presented. Aimed at optimising the desired properties, the microstructure is designed and an alloy composition optimised accordingly, combining criteria based on thermodynamic, thermokinetic and mechanical principles. A genetic algorithm is employed as the optimisation scheme. The approach is applied to the design of ultra-high strength stainless steels. Three composition scenarios, utilising different strengthening precipitates (carbides, Cu and NiAl/Ni₃Ti), are followed. The results are compared to a variety of existing commercial high-end engineering steels, showing that the design strategy presented here may lead to significant improvements in strength beyond current levels.     

Protein folding kinetics and thermodynamics from atomistic simulations

Determining protein folding kinetics and thermodynamics from all-atom molecular dynamics (MD) simulations without using experimental data represents a formidable scientific challenge because simulations can easily get trapped in local minima on rough free energy landscapes. This necessitates the computation of multiple simulation trajectories, which can be independent from each other or coupled in some manner, as, for example, in the replica exchange MD method. Here we present results obtained with a new analysis tool that allows the deduction of faithful kinetics data from a heterogeneous ensemble of simulation trajectories. The method is demonstrated on the decapeptide Chignolin for which we predict folding and unfolding time constants of 1.0 +/- 0.3 and 2.6 +/- 0.4 micros, respectively. We also derive the energetics of folding, and calculate a realistic melting curve for Chignolin.     

Tin in silicate glasses: structure, thermodynamics and kinetics

In this work Mössbauer spectroscopy is used to investigate the oxidation states and structures of tin in silicate glasses. Thermal treatment of the glasses in atmospheres with varying oxygen partial pressure leads to the simultaneous appearance of reduction and diffusion. Experiments with varying treatment time give the opportunity to study diffusion and reduction processes in detail. Comparison of the hyperfine parameters of reference materials with measured parameter provides information about the local surroundings of the tin atoms. An octahedral surrounding for Sn^4?+? is presumed, while Sn^2?+? and three oxygen atoms form a tetrahedral coordination.