Steepest Entropy Ascent Model for Far-Non-Equilibrium Thermodynamics. Unified Implementation of the Maximum Entropy Production Principle

By suitable reformulations, we cast the mathematical frameworks of several well-known different approaches to the description of non-equilibrium dynamics into a unified formulation, which extends to such frameworks the concept of Steepest Entropy Ascent (SEA) dynamics introduced by the present author in previous works on quantum thermodynamics. The present formulation constitutes a generalization also for the quantum thermodynamics framework. In the SEA modeling principle a key role is played by the geometrical metric with respect to which to measure the length of a trajectory in state space. In the near equilibrium limit, the metric tensor is related to the Onsager's generalized resistivity tensor. Therefore, through the identification of a suitable metric field which generalizes the Onsager generalized resistance to the arbitrarily far non-equilibrium domain, most of the existing theories of non-equilibrium thermodynamics can be cast in such a way that the state exhibits a spontaneous tendency to evolve in state space along the path of SEA compatible with the conservation constraints and the boundary conditions. The resulting unified family of SEA dynamical models is intrinsically and strongly consistent with the second law of thermodynamics. Non-negativity of the entropy production is a readily proved general feature of SEA dynamics. In several of the different approaches to non-equilibrium description we consider here, the SEA concept has not been investigated before. We believe it defines the precise meaning and the domain of general validity of the so-called Maximum Entropy Production Principle. It is hoped that the present unifying approach may prove useful in providing a fresh basis for effective, thermodynamically consistent, numerical models and theoretical treatments of irreversible conservative relaxation towards equilibrium from far non-equilibrium states.Comment: 15 pages, 4 figures, to appear in Physical Review

Entropy and Entropy Production in Multiscale Dynamics

Heat conduction is investigated on three levels: equilibrium, Fourier, and Cattaneo. The Fourier level is either the point of departure for investigating the approach to equilibrium or the final stage in the investigation of the approach from the Cattaneo level. Both investigations bring to the Fourier level an entropy and a thermodynamics. In the absence of external and internal influences preventing the approach to equilibrium the entropy that arises in the latter investigation is the production of the classical entropy that arises in the former investigation. If the approach to equilibrium is prevented, then the entropy that arises in the investigation of the approach from the Cattaneo level to the Fourier level still brings to the Fourier level the entropy and the thermodynamics even if the classical entropy and the classical thermodynamics is absent. We also note that vanishing total entropy production as a characterization of equilibrium state is insufficient.Comment: Submitted to the Journal of Non-equilibrium Thermodynamic

Autonomous engines driven by active matter: Energetics and design principles

Because of its nonequilibrium character, active matter in a steady state can drive engines that autonomously deliver work against a constant mechanical force or torque. As a generic model for such an engine, we consider systems that contain one or several active components and a single passive one that is asymmetric in its geometrical shape or its interactions. Generally, one expects that such an asymmetry leads to a persistent, directed current in the passive component, which can be used for the extraction of work. We validate this expectation for a minimal model consisting of an active and a passive particle on a one-dimensional lattice. It leads us to identify thermodynamically consistent measures for the efficiency of the conversion of isotropic activity to directed work. For systems with continuous degrees of freedom, work cannot be extracted using a one-dimensional geometry under quite general conditions. In contrast, we put forward two-dimensional shapes of a movable passive obstacle that are best suited for the extraction of work, which we compare with analytical results for an idealised work-extraction mechanism. For a setting with many noninteracting active particles, we use a mean-field approach to calculate the power and the efficiency, which we validate by simulations. Surprisingly, this approach reveals that the interaction with the passive obstacle can mediate cooperativity between otherwise noninteracting active particles, which enhances the extracted power per active particle significantly.Comment: 21 pages, 8 figure

Mesoscopic modeling of a two-phase flow in the presence of boundaries: the Contact Angle

We present a mesoscopic model, based on the Boltzmann Equation, for the interaction between a solid wall and a non-ideal fluid. We present an analytic derivation of the contact angle in terms of the surface tension between the liquid-gas, the liquid-solid and the gas-solid phases. We study the dependency of the contact angle on the two free parameters of the model, which determine the interaction between the fluid and the boundaries, i.e. the equivalent of the wall density and of the wall-fluid potential in Molecular Dynamics studies. We compare the analytical results obtained in the hydrodynamical limit for the density profile and for the surface tension expression with the numerical simulations. We compare also our two-phase approach with some exact results for a pure hydrodynamical incompressible fluid based on Navier-Stokes equations with boundary conditions made up of alternating slip and no-slip strips. Finally, we show how to overcome some theoretical limitations connected with a discretized Boltzmann scheme and we discuss the equivalence between the surface tension defined in terms of the mechanical equilibrium and in terms of the Maxwell construction.Comment: 29 pages, 12 figure

Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions

Previous and present "academic" research aiming at atomic scale understanding is mainly concerned with the study of individual molecular processes possibly underlying materials science applications. Appealing properties of an individual process are then frequently discussed in terms of their direct importance for the envisioned material function, or reciprocally, the function of materials is somehow believed to be understandable by essentially one prominent elementary process only. What is often overlooked in this approach is that in macroscopic systems of technological relevance typically a large number of distinct atomic scale processes take place. Which of them are decisive for observable system properties and functions is then not only determined by the detailed individual properties of each process alone, but in many, if not most cases also the interplay of all processes, i.e. how they act together, plays a crucial role. For a "predictive materials science modeling with microscopic understanding", a description that treats the statistical interplay of a large number of microscopically well-described elementary processes must therefore be applied. Modern electronic structure theory methods such as DFT have become a standard tool for the accurate description of individual molecular processes. Here, we discuss the present status of emerging methodologies which attempt to achieve a (hopefully seamless) match of DFT with concepts from statistical mechanics or thermodynamics, in order to also address the interplay of the various molecular processes. The new quality of, and the novel insights that can be gained by, such techniques is illustrated by how they allow the description of crystal surfaces in contact with realistic gas-phase environments.Comment: 24 pages including 17 figures, related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Mesoscopic non-equilibrium thermodynamics approach to non-Debye dielectric relaxation

Mesoscopic non-equilibrium thermodynamics is used to formulate a model describing non-homogeneous and non-Debye dielectric relaxation. The model is presented in terms of a Fokker-Planck equation for the probability distribution of non-interacting polar molecules in contact with a heat bath and in the presence of an external time-dependent electric field. Memory effects are introduced in the Fokker-Planck description through integral relations containing memory kernels, which in turn are used to establish a connection with fractional Fokker-Planck descriptions. The model is developed in terms of the evolution equations for the first two moments of the distribution function. These equations are solved by following a perturbative method from which the expressions for the complex susceptibilities are obtained as a functions of the frequency and the wave number. Different memory kernels are considered and used to compare with experiments of dielectric relaxation in glassy systems. For the case of Cole-Cole relaxation, we infer the distribution of relaxation times and its relation with an effective distribution of dipolar moments that can be attributed to different segmental motions of the polymer chains in a melt.Comment: 33 pages, 6 figure

Thermodynamic length in open quantum systems

The dissipation generated during a quasistatic thermodynamic process can be characterised by introducing a metric on the space of Gibbs states, in such a way that minimally-dissipating protocols correspond to geodesic trajectories. Here, we show how to generalize this approach to open quantum systems by finding the thermodynamic metric associated to a given Lindblad master equation. The obtained metric can be understood as a perturbation over the background geometry of equilibrium Gibbs states, which is induced by the Kubo-Mori-Bogoliubov (KMB) inner product. We illustrate this construction on two paradigmatic examples: an Ising chain and a two-level system interacting with a bosonic bath with different spectral densities.Comment: 22 pages, 3 figures. v5: minor corrections, accepted in Quantu