Showing papers on "Non-equilibrium thermodynamics published in 2015"

Macroscopic fluctuation theory

Abstract: The statistical mechanics of systems out of equilibrium provides a formidable challenge. This review describes an approach to a subset of such problems, viz., stationary nonequilibrium states. The review includes what is known as the macroscopic fluctuation theory, which allows for the definition of nonequilibrium analogs of thermodynamics potentials, and is applied to various illustrative models.

Towards quantum thermodynamics in electronic circuits

Abstract: Electronic circuits operating at sub-kelvin temperatures are attractive candidates for studying classical and quantum thermodynamics: their temperature can be controlled and measured locally with exquisite precision, and they allow experiments with large statistical samples. The availability and rapid development of devices such as quantum dots, single-electron boxes and superconducting qubits only enhance their appeal. But although these systems provide fertile ground for studying heat transport, entropy production and work in the context of quantum mechanics, the field remains in its infancy experimentally. Here, we review some recent experiments on quantum heat transport, fluctuation relations and implementations of Maxwell’s demon, revealing the rich physics yet to be fully probed in these systems. Experiments probing non-equilibrium processes have so far been tailored largely to classical systems. The endeavour to extend our understanding into the quantum realm is finding traction in studies of electronic circuits at sub-kelvin temperatures.

Towards a thermodynamics of active matter

Abstract: Self-propulsion allows living systems to display self-organization and unusual phase behavior. Unlike passive systems in thermal equilibrium, active matter systems are not constrained by conventional thermodynamic laws. A question arises, however, as to what extent, if any, can concepts from classical thermodynamics be applied to nonequilibrium systems like active matter. Here we use the new swim pressure perspective to develop a simple theory for predicting phase separation in active matter. Using purely mechanical arguments we generate a phase diagram with a spinodal and critical point, and define a nonequilibrium chemical potential to interpret the “binodal.” We provide a generalization of thermodynamic concepts like the free energy and temperature for nonequilibrium active systems. Our theory agrees with existing simulation data both qualitatively and quantitatively and may provide a framework for understanding and predicting the behavior of nonequilibrium active systems.

Solvation thermodynamics of organic molecules by the molecular integral equation theory: approaching chemical accuracy

Abstract: The integral equation theory (IET) of molecular liquids has been an active area of academic research in theoretical and computational physical chemistry for over 40 years because it provides a consistent theoretical framework to describe the structural and thermodynamic properties of liquid-phase solutions. The theory can describe pure and mixed solvent systems (including anisotropic and nonequilibrium systems) and has already been used for theoretical studies of a vast range of problems in chemical physics / physical chemistry, molecular biology, colloids, soft matter, and electrochemistry. A consider- able advantage of IET is that it can be used to study speci fi c solute − solvent interactions, unlike continuum solvent models, but yet it requires considerably less computational expense than explicit solvent simulations.

Quantum Thermodynamics: A Nonequilibrium Green’s Function Approach

Abstract: We establish the foundations of a nonequilibrium theory of quantum thermodynamics for noninteracting open quantum systems strongly coupled to their reservoirs within the framework of the nonequilibrium Green's functions. The energy of the system and its coupling to the reservoirs are controlled by a slow external time-dependent force treated to first order beyond the quasistatic limit. We derive the four basic laws of thermodynamics and characterize reversible transformations. Stochastic thermodynamics is recovered in the weak coupling limit.

Irreversibility and the Arrow of Time in a Quenched Quantum System

Abstract: Irreversibility is one of the most intriguing concepts in physics. While microscopic physical laws are perfectly reversible, macroscopic average behavior has a preferred direction of time. According to the second law of thermodynamics, this arrow of time is associated with a positive mean entropy production. Using a nuclear magnetic resonance setup, we measure the nonequilibrium entropy produced in an isolated spin-1/2 system following fast quenches of an external magnetic field. We experimentally demonstrate that it is equal to the entropic distance, expressed by the Kullback-Leibler divergence, between a microscopic process and its time reversal. Our result addresses the concept of irreversibility from a microscopic quantum standpoint.

Nonequilibrium statistical mechanics of mixtures of particles in contact with different thermostats.

Abstract: We introduce a novel type of locally driven systems made of two types of particles (or a polymer with two types of monomers) subject to a chaotic drive with approximately white noise spectrum, but different intensity; in other words, particles of different types are in contact with thermostats at different temperatures. We present complete systematic statistical mechanics treatment starting from first principles. Although we consider only corrections to the dilute limit due to pairwise collisions between particles, meaning we study a nonequilibrium analog of the second virial approximation, we find that the system exhibits a surprisingly rich behavior. In particular, pair correlation function of particles has an unusual quasi-Boltzmann structure governed by an effective temperature distinct from that of any of the two thermostats. We also show that at sufficiently strong drive the uniformly mixed system becomes unstable with respect to steady states consisting of phases enriched with different types of particles. In the second virial approximation, we define nonequilibrium "chemical potentials" whose gradients govern diffusion fluxes and a nonequilibrium "osmotic pressure," which governs the mechanical stability of the interface.

Equilibrium electroconvective instability.

Abstract: Since its prediction 15 years ago, hydrodynamic instability in concentration polarization at a charge-selective interface has been attributed to nonequilibrium electro-osmosis related to the extended space charge which develops at the limiting current. This attribution had a double basis. On the one hand, it has been recognized that neither equilibrium electro-osmosis nor bulk electroconvection can yield instability for a perfectly charge-selective solid. On the other hand, it has been shown that nonequilibrium electro-osmosis can. The first theoretical studies in which electro-osmotic instability was predicted and analyzed employed the assumption of perfect charge selectivity for the sake of simplicity and so did the subsequent studies of various time-dependent and nonlinear features of electro-osmotic instability. In this Letter, we show that relaxing the assumption of perfect charge selectivity (tantamount to fixing the electrochemical potential of counterions in the solid) allows for the equilibrium electroconvective instability. In addition, we suggest a simple experimental test for determining the true, either equilibrium or nonequilibrium, origin of instability in concentration polarization.

Nature of heat in strongly coupled open quantum systems

Abstract: We show that any heat definition expressed as an energy change in the reservoir energy plus any fraction of the system-reservoir interaction is not an exact differential when evaluated along reversible isothermal transformations, except when that fraction is zero. Even in that latter case the reversible heat divided by temperature, namely entropy, does not satisfy the third law of thermodynamics and diverges in the low temperature limit. These results are found within the framework of nonequilibrium Green functions (NEGF) using a single level quantum dot strongly coupled to fermionic reservoirs and subjected to a time-dependent protocol modulating the dot energy as well as the dot-reservoir coupling strength.

Equivalence and Nonequivalence of Ensembles: Thermodynamic, Macrostate, and Measure Levels

Abstract: We present general and rigorous results showing that the microcanonical and canonical ensembles are equivalent at all three levels of description considered in statistical mechanics—namely, thermodynamics, equilibrium macrostates, and microstate measures—whenever the microcanonical entropy is concave as a function of the energy density in the thermodynamic limit. This is proved for any classical many-particle systems for which thermodynamic functions and equilibrium macrostates exist and are defined via large deviation principles, generalizing many previous results obtained for specific classes of systems and observables. Similar results hold for other dual ensembles, such as the canonical and grand-canonical ensembles, in addition to trajectory or path ensembles describing nonequilibrium systems driven in steady states.

Lattice Boltzmann approach for complex nonequilibrium flows.

Abstract: We present a lattice Boltzmann realization of Grad's extended hydrodynamic approach to nonequilibrium flows. This is achieved by using higher-order isotropic lattices coupled with a higher-order regularization procedure. The method is assessed for flow across parallel plates and three-dimensional flows in porous media, showing excellent agreement of the mass flow with analytical and numerical solutions of the Boltzmann equation across the full range of Knudsen numbers, from the hydrodynamic regime to ballistic motion.

Why Do Cities Grow? Insights from Nonequilibrium Thermodynamics at the Urban and Global Scales

Abstract: This forum article explores thermodynamic understanding of the growth of cities, including theoretical foundations, observations, and analysis. The general theory of nonequilibrium thermodynamics is reviewed, recognizing differences in interpretation between Prigogine and Schneider and Kay as well as discussing the hypothesis of maximum entropy production. Calculations of exergy gradients in a few cities and settlements, along with measures of anthropogenic heat loss in further cities, support the notion that cities are dissipative structures. The observation that primary energy use per capita increases in Singapore and Hong Kong as they grow is further evidence to support the thermodynamic understanding of the growth of cities, indicative of an increasing rate of entropy production. At the global scale, the strong linear relationship between global urban population and total global energy use, and the distribution of city sizes according to Zipf's law, can be understood as emergent results based on thermodynamics. Parallel results might be derived from models that represent underlying microscale processes, several of which are reviewed. Issues for future research include: development of nonequilibrium thermodynamic models specific to city growth; further study of exergy flows of cities with consistent methodology, including attention to solar energy exchanges in cities; and further exploration of links between thermodynamic and economic models of urban growth.

A measure of majorization emerging from single-shot statistical mechanics

Abstract: The use of the von Neumann entropy in formulating the laws of thermodynamics has recently been challenged. It is associated with the average work whereas the work guaranteed to be extracted in any single run of an experiment is the more interesting quantity in general. We show that an expression that quantifies majorization determines the optimal guaranteed work. We argue it should therefore be the central quantity of statistical mechanics, rather than the von Neumann entropy. In the limit of many identical and independent subsystems (asymptotic i.i.d) the von Neumann entropy expressions are recovered but in the non-equilbrium regime the optimal guaranteed work can be radically different to the optimal average. Moreover our measure of majorization governs which evolutions can be realized via thermal interactions, whereas the non-decrease of the von Neumann entropy is not sufficiently restrictive. Our results are inspired by single-shot information theory.

Multiple-relaxation-time lattice Boltzmann kinetic model for combustion

Abstract: To probe both the hydrodynamic nonequilibrium (HNE) and thermodynamic nonequilibrium (TNE) in the combustion process, a two-dimensional multiple-relaxation-time (MRT) version of lattice Boltzmann kinetic model (LBKM) for combustion phenomena is presented. The chemical energy released in the progress of combustion is dynamically coupled into the system by adding a chemical term to the LB kinetic equation. Aside from describing the evolutions of the conserved quantities, the density, momentum, and energy, which are what the Navier-Stokes model describes, the MRT-LBKM presents also a coarse-grained description on the evolutions of some nonconserved quantities. The current model works for both subsonic and supersonic flows with or without chemical reaction. In this model, both the specific-heat ratio and the Prandtl number are flexible, the TNE effects are naturally presented in each simulation step. The model is verified and validated via well-known benchmark tests. As an initial application, various nonequilibrium behaviors, including the complex interplays between various HNEs, between various TNEs, and between the HNE and TNE, around the detonation wave in the unsteady and steady one-dimensional detonation processes are preliminarily probed. It is found that the system viscosity (or heat conductivity) decreases the local TNE, but increases the global TNE around the detonation wave, that even locally, the system viscosity (or heat conductivity) results in two kinds of competing trends, to increase and to decrease the TNE effects. The physical reason is that the viscosity (or heat conductivity) takes part in both the thermodynamic and hydrodynamic responses.

Non-equilibrium gas–liquid interface dynamics in high-pressure liquid injection systems

Abstract: The transition of classical spray atomization processes to single-phase continuous dense-fluid mixing dynamics with diminished surface tension forces is poorly understood. Recently, a theory has been presented that established, based on a Knudsen-number criterion, that the development of such mixing layers is initiated because the multicomponent two-phase interface becomes much wider than the mean free molecular path. This shows that the transition to mixing layers occurs due to interfacial dynamics and not, as conventional wisdom had suggested, because the liquid phase has heated up to supercritical temperatures where surface tension forces diminish. In this paper we focus on the dynamics of this transition process, which still poses many fundamental questions. We show that such dynamics are dictated by substantial statistical fluctuations about the average interface molecule number and the presence of significant interfacial free energy forces. The comprehensive analysis is performed based on a combination of non-equilibrium mean-field thermodynamics and a detailed modified 32-term Benedict–Webb–Rubin mixture state equation. Statistical fluctuations are quantified using the generally accepted model of Poisson-distributions for variances in systems with a small number of molecules. Such fluctuations quantify the range of pressure and temperature conditions under which the gradual transition to dense-fluid mixing dynamics occurs. The interface begins to deteriorate as it broadens substantially. The related interfacial free energy forces do not instantly diminish only because vapor–liquid equilibrium conditions do not apply anymore. Instead, such forces along with the present interfacial statistical fluctuations are shown to gradually decrease as the interface transitions through the molecular chaos regime and to diminish once the interface enters the continuum regime. Then, the interfacial region becomes a continuous gas–liquid mixing layer with diminished free energy forces that is significantly affected by single-phase real-fluid thermodynamics and transport properties.

Stochastic Independence as a Resource in Small-Scale Thermodynamics

Abstract: It is well known in thermodynamics that the creation of correlations costs work. It seems then a truism that if a thermodynamic transformation A→B is impossible, so will be any transformation that in sending A to B also correlates among them some auxiliary systems C. Surprisingly, we show that this is not the case for nonequilibrium thermodynamics of microscopic systems. On the contrary, the creation of correlations greatly extends the set of accessible states, to the point that we can perform on individual systems and in a single shot any transformation that would otherwise be possible only if the number of systems involved was very large. We also show that one only ever needs to create a vanishingly small amount of correlations (as measured by mutual information) among a small number of auxiliary systems (never more than three). The many, severe constraints of microscopic thermodynamics are reduced to the sole requirement that the nonequilibrium free energy decreases in the transformation. This shows that, in principle, reliable extraction of work equal to the free energy of a system can be performed by microscopic engines.

A theory for the phase behavior of mixtures of active particles

Abstract: Systems at equilibrium like molecular or colloidal suspensions have a well-defined thermal energy kBT that quantifies the particles' kinetic energy and gauges how "hot" or "cold" the system is. For systems far from equilibrium, such as active matter, it is unclear whether the concept of a "temperature" exists and whether self-propelled entities are capable of thermally equilibrating like passive Brownian suspensions. Here we develop a simple mechanical theory to study the phase behavior and "temperature" of a mixture of self-propelled particles. A mixture of active swimmers and passive Brownian particles is an ideal system for discovery of the temperature of active matter and the quantities that get shared upon particle collisions. We derive an explicit equation of state for the active/passive mixture to compute a phase diagram and to generalize thermodynamic concepts like the chemical potential and free energy for a mixture of nonequilibrium species. We find that different stability criteria predict in general different phase boundaries, facilitating considerations in simulations and experiments about which ensemble of variables are held fixed and varied.

Stochastic approach to equilibrium and nonequilibrium thermodynamics.

Abstract: We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

Optimal control of overdamped systems

Abstract: Nonequilibrium physics encompasses a broad range of natural and synthetic small-scale systems. Optimizing transitions of such systems will be crucial for the development of nanoscale technologies and may reveal the physical principles underlying biological processes at the molecular level. Recent work has demonstrated that when a thermodynamic system is driven away from equilibrium then the space of controllable parameters has a Riemannian geometry induced by a generalized inverse diffusion tensor. We derive a simple, compact expression for the inverse diffusion tensor that depends solely on equilibrium information for a broad class of potentials. We use this formula to compute the minimal dissipation for two model systems relevant to small-scale information processing and biological molecular motors. In the first model, we optimally erase a single classical bit of information modeled by an overdamped particle in a smooth double-well potential. In the second model, we find the minimal dissipation of a simple molecular motor model coupled to an optical trap. In both models, we find that the minimal dissipation for the optimal protocol of duration τ is proportional to 1/τ, as expected, though the dissipation for the erasure model takes a different form than what we found previously for a similar system.

Non-linear extended thermodynamics of real gases with 6 fields

Abstract: We establish extended thermodynamics (ET) of real gases with 6 independent fields, i.e., the mass density, the velocity, the temperature and the dynamic pressure, without adopting the near-equilibrium approximation. We prove its compatibility with the universal principles (the entropy principle, the Galilean invariance and the stability), and obtain the symmetric hyperbolic system with respect to the main field. In near-equilibrium we recover the previous results. The correspondence between the ET 6-field theory and Meixner׳s theory of relaxation processes is discovered. The internal variable and the non-equilibrium temperature in Meixner׳s theory are expressed in terms of the quantities of the ET 6-field theory, in particular, the dynamic pressure. As an example, we present the cases of a rarefied polyatomic gas and study the monatomic-gas limit where the system converges to the Euler system of a perfect fluid.

Thermostat for nonequilibrium multiparticle-collision-dynamics simulations

Abstract: Multiparticle collision dynamics (MPC), a particle-based mesoscale simulation technique for complex fluid, is widely employed in nonequilibrium simulations of soft matter systems. To maintain a defined thermodynamic state, thermalization of the fluid is often required for certain MPC variants. We investigate the influence of three thermostats on the nonequilibrium properties of a MPC fluid under shear or in Poiseuille flow. In all cases, the local velocities are scaled by a factor, which is either determined via a local simple scaling approach (LSS), a Monte Carlo-like procedure (MCS), or by the Maxwell-Boltzmann distribution of kinetic energy (MBS). We find that the various scaling schemes leave the flow profile unchanged and maintain the local temperature well. The fluid viscosities extracted from the various simulations are in close agreement. Moreover, the numerically determined viscosities are in remarkably good agreement with the respective theoretically predicted values. At equilibrium, the calculation of the dynamic structure factor reveals that the MBS method closely resembles an isothermal ensemble, whereas the MCS procedure exhibits signatures of an adiabatic system at larger collision-time steps. Since the velocity distribution of the LSS approach is non-Gaussian, we recommend to apply the MBS thermostat, which has been shown to produce the correct velocity distribution even under nonequilibrium conditions.

Thermodynamics and statistical mechanics : an integrated approach

Abstract: 1. Introduction and guide to this text 2. Equilibrium and entropy 3. Energy and how the microscopic world works 4. Entropy and how the macroscopic world works 5. The fundamental equation 6. The first law and reversibility 7. Legendre transforms and other potentials 8. Maxwell relations and measurable quantities 9. Gases 10. Phase equilibrium 11. Stability 12. Solutions - fundamentals 13. Solutions - advanced and special cases 14. Solids 15. The third law 16. The canonical partition function 17. Fluctuations 18. Statistical mechanics of classical systems 19. Other ensembles 20. Reaction equilibrium 21. Reaction coordinates and rates 22. Molecular simulation methods.

Relativistic quantum transport coefficients for second-order viscous hydrodynamics

Abstract: We express the transport coefficients appearing in the second-order evolution equations for bulk viscous pressure and shear stress tensor using Bose-Einstein, Boltzmann, and Fermi-Dirac statistics for the equilibrium distribution function and Grad's 14-moment approximation as well as the method of Chapman-Enskog expansion for the nonequilibrium part. Focusing on the case of transversally homogeneous and boost-invariant longitudinal expansion of the viscous medium, we compare the results obtained using the above methods with those obtained from the exact solution of the massive 0+$1d$ relativistic Boltzmann equation in the relaxation-time approximation. We show that compared to the 14-moment approximation, the hydrodynamic transport coefficients obtained by employing the Chapman-Enskog method lead to better agreement with the exact solution of the relativistic Boltzmann equation.

Random bursts determine dynamics of active filaments

Abstract: Constituents of living or synthetic active matter have access to a local energy supply that serves to keep the system out of thermal equilibrium. The statistical properties of such fluctuating active systems differ from those of their equilibrium counterparts. Using the actin filament gliding assay as a model, we studied how nonthermal distributions emerge in active matter. We found that the basic mechanism involves the interplay between local and random injection of energy, acting as an analog of a thermal heat bath, and nonequilibrium energy dissipation processes associated with sudden jump-like changes in the system’s dynamic variables. We show here how such a mechanism leads to a nonthermal distribution of filament curvatures with a non-Gaussian shape. The experimental curvature statistics and filament relaxation dynamics are reproduced quantitatively by stochastic computer simulations and a simple kinetic model.

Analysis of slow transitions between nonequilibrium steady states

Abstract: Transitions between nonequilibrium steady states obey a generalized Clausius inequality, which becomes an equality in the quasistatic limit. For slow but finite transitions, we show that the behavior of the system is described by a response matrix whose elements are given by a far-from-equilibrium Green-Kubo formula, involving the decay of correlations evaluated in the nonequilibrium steady state. This result leads to a fluctuation-dissipation relation between the mean and variance of the nonadiabatic entropy production, $\Delta s_{\rm na}$. Furthermore, our results extend -- to nonequilibrium steady states -- the thermodynamic metric structure introduced by Sivak and Crooks for analyzing minimal-dissipation protocols for transitions between equilibrium states.

First-principles calculation of the thermoelectric figure of merit for [2,2]paracyclophane-based single-molecule junctions

Abstract: Here we present a theoretical study of the thermoelectric transport through {[}2,2{]}para\-cyclo\-phane-based single-molecule junctions. Combining electronic and vibrational structures, obtained from density functional theory (DFT), with nonequilibrium Green's function techniques, allows us to treat both electronic and phononic transport properties at a first-principles level. For the electronic part, we include an approximate self-energy correction, based on the DFT+$\Sigma$ approach. This enables us to make a reliable prediction of all linear response transport coefficients entering the thermoelectric figure of merit $ZT$. Paracyclophane derivatives offer a great flexibility in tuning their chemical properties by attaching different functional groups. We show that, for the specific molecule, the functional groups mainly influence the thermopower, allowing to tune its sign and absolute value. We predict that the functionalization of the bare paracyclophane leads to a largely enhanced electronic contribution $Z_{\mathrm{el}}T$ to the figure of merit. Nevertheless, the high phononic contribution to the thermal conductance strongly suppresses $ZT$. Our work demonstrates the importance to include the phonon thermal conductance for any realistic estimate of the $ZT$ for off-resonant molecular transport junctions. In addition, it shows the possibility of a chemical tuning of the thermoelectric properties for a series of available molecules, leading to equally performing hole- and electron-conducting junctions based on the same molecular framework.

Ab Initio Nonequilibrium Thermodynamic and Transport Properties of Ultrafast Laser Irradiated 316L Stainless Steel

Abstract: We present calculations of transient behavior of thermodynamic and transport coefficients on the time scale of electron–phonon relaxation upon ultrashort laser excitation of ferrous alloys. Their role defining energy deposition and primary microscopic material response to the laser irradiation is outlined. Nonequilibrium thermodynamic properties of 316L stainless steel are determined from first-principles calculations. Taking into account the complexity of multimetallic materials, the density functional theory is first applied to describe the electronic density of states of an alloy stainless steel matrix as a function of electronic heating. An increase of the localization degree of the charge density was found to be responsible for the modification of the electronic structure upon electronic heating, with consequences on chemical potential, electronic capacity, and pressure. It is shown that the electronic temperature dependence of stainless steel thermodynamic properties are consistent with the behavior...