Comparative analysis of fluctuations in viscoelastic stress: A comparison of the temporary network and dumbbell models.

Traditionally, stress fluctuations in flowing and deformed materials are overlooked, with an obvious focus on average stresses in a continuum mechanical approximation. However, these fluctuations, often dismissed as "noise," hold the potential to provide direct insights into the material structure and its structure-stress coupling, uncovering detailed aspects of fluid transport and relaxation behaviors. Despite advancements in experimental techniques allowing for the visualization of these fluctuations, their significance remains largely untapped as modeling efforts continue to target Newtonian fluids within the confines of Gaussian noise assumptions. In the present work, a comparative analysis of stress fluctuations in two distinct microstructural models is carried out: the temporary network model and the hydrodynamic dumbbell model. Despite both models conforming to the upper convected Maxwell model at a macroscopic level, the temporary network model predicts non-Gaussian fluctuations. We find that stress fluctuations within the temporary network model exhibit more pronounced abruptness at the local scale, with only an enlargement of the control volume leading to a gradual Gaussian-like noise, diminishing the differences between the two models. These findings underscore the heightened sensitivity of fluctuating rheology to microstructural details and the microstructure-flow coupling, beyond what is captured by macroscopically averaged stresses.

Nonequilibrium liquid-vapor interfaces: Linear and nonlinear descriptions.

While it is often assumed that liquid-vapor interfaces in nonequilibrium processes are in states of local thermodynamic equilibrium, this might not be the case for strong deviations from equilibrium. Clausius-Clapeyron equations for bulk properties yield a consistently defined temperature of the interface that is close to the liquid bulk temperature. The alternative interface temperature defined through the surface tension will be different for stronger nonequilibrium processes. Structural variables are introduced to extend the thermodynamic description of interfaces to a wider range of processes. Interfacial resistivities will depend on interface temperature as well as mass and heat flux through the interface.

Nonequilibrium statistical thermodynamics of multicomponent interfaces.

Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the "sharp" interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.

Direct calculation of the functional inverse of realistic interatomic potentials in field-theoretic simulations.

We discuss the functional inverse problem in field-theoretic simulations for realistic pairwise potentials such as the Morse potential (widely used in particle simulations as an alternative to the 12-6 Lennard-Jones one), and we propose the following two solutions: (a) a numerical one based on direct inversion on a regular grid or deconvolution and (b) an analytical one by expressing attractive and repulsive contributions to the Morse potential as higher-order derivatives of the Dirac delta function; the resulting system of ordinary differential equations in the saddle-point approximation is solved numerically with appropriate model-consistent boundary conditions using a Newton-Raphson method. For the first time, exponential-like, physically realistic pair interactions are analytically treated and incorporated into a field-theoretic framework. The advantages and disadvantages of the two approaches are discussed in detail in connection with numerical findings from test simulations for the radial distribution function of a monatomic fluid at realistic densities providing direct evidence for the capability of the analytical method to resolve structural features down to the Angstrom scale.

Field-theoretic simulations beyond δ-interactions: Overcoming the inverse potential problem in auxiliary field models.

Modern field-theoretic simulations of complex fluids and polymers are constructed around a particle-to-field transformation that brings an inverse potential u-1 in the model equations. This has restricted the application of the framework to systems characterized by relatively simple pairwise interatomic interactions; for example, excluded volume effects are treated through the use of δ-function interactions. In this study, we first review available nonbonded pair interactions in field-theoretic models and propose a classification. Then, we outline the inverse potential problem and present an alternative approach on the basis of a saddle-point approximation, enabling the use of a richer set of pair interaction functions. We test our approach by using as an example the Morse potential, which finds extensive applications in particle-based simulations, and we calibrate u-1 with results from a molecular dynamics simulation. The u-1 thus obtained is consistent with the field-theoretic model equations, and when used in stand-alone self-consistent field simulations, it produces the correct fluid structure starting from a random initial state of the density field.

The dissipative approach to quantum field theory: conceptual foundations and ontological implications.

Many attempts have been made to provide Quantum Field Theory with conceptually clear and mathematically rigorous foundations; remarkable examples are the Bohmian and the algebraic perspectives respectively. In this essay we introduce the dissipative approach to QFT, a new alternative formulation of the theory explaining the phenomena of particle creation and annihilation starting from nonequilibrium thermodynamics. It is shown that DQFT presents a rigorous mathematical structure, and a clear particle ontology, taking the best from the mentioned perspectives. Finally, after the discussion of its principal implications and consequences, we compare it with the main Bohmian QFTs implementing a particle ontology.

Formulation of moment equations for rarefied gases within two frameworks of non-equilibrium thermodynamics: RET and GENERIC.

In this work, we make a further step in bringing together different approaches to non-equilibrium thermodynamics. The structure of the moment hierarchy derived from the Boltzmann equation is at the heart of rational extended thermodynamics (RET, developed by Ingo Müller and Tommaso Ruggeri). Whereas the full moment hierarchy has the structure expressed in the general equation for the nonequilibrium reversible-irreversible coup- ling (GENERIC), the Poisson bracket structure of reversible dynamics postulated in that approach is a major obstacle for truncating moment hierarchies, which seems to work only in exceptional cases (most importantly, for the five moments associated with conservation laws). The practical importance of truncated moment hierarchies in rarefied gas dynamics and microfluidics motivates us to develop a new strategy for establishing the full GENERIC structure of truncated moment equations, based on non-entropy-producing irreversible processes associated with Casimir symmetry. Detailed results are given for the special case of 10 moments. This article is part of the theme issue 'Fundamental aspects of nonequilibrium thermodynamics'.

Structure-preserving integrators for dissipative systems based on reversible- irreversible splitting.

We study the optimal design of numerical integrators for dissipative systems, for which there exists an underlying thermodynamic structure known as GENERIC (general equation for the nonequilibrium reversible-irreversible coupling). We present a frame-work to construct structure-preserving integrators by splitting the system into reversible and irreversible dynamics. The reversible part, which is often degenerate and reduces to a Hamiltonian form on its symplectic leaves, is solved by using a symplectic method (e.g. Verlet) with degenerate variables being left unchanged, for which an associated modified Hamiltonian (and subsequently a modified energy) in the form of a series expansion can be obtained by using backward error analysis. The modified energy is then used to construct a modified friction matrix associated with the irreversible part in such a way that a modified degeneracy condition is satisfied. The modified irreversible dynamics can be further solved by an explicit midpoint method if not exactly solvable. Our findings are verified by various numerical experiments, demonstrating the superiority of structure-preserving integrators over alternative schemes in terms of not only the accuracy control of both energy conservation and entropy production but also the preservation of the conformal symplectic structure in the case of linearly damped systems.

Stability analysis for a thermodynamically consistent model of relativistic fluid dynamics.

In relativistic fluid mechanics, positive entropy production is known to be insufficient for guaranteeing stability. Much stronger criteria for thermodynamic admissibility have become available in nonequilibrium thermodynamics. We here perform a linear stability analysis for a model of relativistic hydrodynamics that is based on the general equation for the nonequilibrium reversible-irreversible coupling (GENERIC) framework of nonequilibrium thermodynamics. Assuming a quadratic entropy function near equilibrium, we find stability for the entire range of physically meaningful model parameters for relativistic fluid dynamics based on GENERIC. The search for thermodynamic admissibility moreover reveals a fundamental difference between liquids and gases in relativistic fluid dynamics.

How the World Changes By Going from One- to Two-Dimensional Polymers in Solution.

Scaling behavior of one-dimensional (1D) and two-dimensional (2D) polymers in dilute solution is discussed with the goal of stimulating experimental work by chemists, physicists, and material scientists in the emerging field of 2D polymers. The arguments are based on renormalization-group theory, which is explained for a general audience. Many ideas and methods successfully applied to 1D polymers are found not to work if one goes to 2D polymers. The role of the various states exhibiting universal behavior is turned upside down. It is expected that solubility will be a serious challenge for 2D polymers. Therefore, given the crucial importance of solutions in characterization and processing, synthetic concepts are proposed that allow the local bending rigidity and the molar mass to be tuned and the long-range interactions to be engineered, all with the goal of preventing the polymer from falling into flat or compact states.

Nonequilibrium thermodynamics of an interface.

Interfacial thermodynamics has deep ramifications in understanding the boundary conditions of transport theories. We present a formulation of local equilibrium for interfaces that extends the thermodynamics of the "dividing surface," as introduced by Gibbs, to nonequilibrium settings such as evaporation or condensation. By identifying the precise position of the dividing surface in the interfacial region with a gauge degree of freedom, we exploit gauge-invariance requirements to consistently define the intensive variables for the interface. The model is verified under stringent conditions by employing high-precision nonequilibrium molecular-dynamics simulations of a coexisting vapor-liquid Lennard-Jones fluid. We conclude that the interfacial temperature is determined using the surface tension as a "thermometer," and it can be significantly different from the temperatures of the adjacent phases. Our findings lay foundations for nonequilibrium interfacial thermodynamics.

Two-dimensional polymers: concepts and perspectives.

Creation of polymers comprised of repeat units that can create topologically planar macromolecules (rather than linear) has been the topic of several recent studies in the field of synthetic polymer chemistry. Such novel macromolecules, known as 2D polymers, are the result of advanced synthetic methodology which allows creation of monolayer sheets with a periodic internal structure and functional groups placed at predetermined sites under mild conditions. Given the promising potentials of 2D polymers, this feature paper aims at discussing the concept of these novel macromolecules from a topological viewpoint in Section 1. This is followed by spotlighting the expected behavior of 2D polymers in the context of polymer physics (entropy elasticity, strength, percolation, and persistence) and polymer chemistry (copolymers and growth kinetics) in Section 2. Section 3 delineates synthetic and analytical matters associated with 2D polymers followed by a brief final section highlighting the potential of these sheet-like macromolecules for application purposes. We hope this article will trigger the interest of chemists, physicists and engineers to help develop this encouraging new class of materials further such that societally relevant applications will be accessible in the market soon.

Modelling the rheology of anisotropic particles adsorbed on a two-dimensional fluid interface.

We present a general approach based on nonequilibrium thermodynamics for bridging the gap between a well-defined microscopic model and the macroscopic rheology of particle-stabilised interfaces. Our approach is illustrated by starting with a microscopic model of hard ellipsoids confined to a planar surface, which is intended to simply represent a particle-stabilised fluid-fluid interface. More complex microscopic models can be readily handled using the methods outlined in this paper. From the aforementioned microscopic starting point, we obtain the macroscopic, constitutive equations using a combination of systematic coarse-graining, computer experiments and Hamiltonian dynamics. Exemplary numerical solutions of the constitutive equations are given for a variety of experimentally relevant flow situations to explore the rheological behaviour of our model. In particular, we calculate the shear and dilatational moduli of the interface over a wide range of surface coverages, ranging from the dilute isotropic regime, to the concentrated nematic regime.

Preservation of thermodynamic structure in model reduction.

Based on the availability of an invariant manifold, we develop a model-reduction procedure that preserves thermodynamic structure. More concretely, we construct the Poisson and irreversible brackets of the general equation for the nonequilibrium reversible-irreversible coupling of nonequilibrium thermodynamics by means of the ideas originally introduced for handling constraints. The general ideas are then applied to the Kramers problem, that is, the description of transitions between two potential wells separated by a high barrier. This example reveals how a fortuitous cancellation mechanism that allows a logarithmic entropy to generate a linear diffusion equation is inherited by a master equation resulting from model reduction.

Irreversible dynamics, Onsager-Casimir symmetry, and an application to turbulence.

Irreversible contributions to the dynamics of nonequilibrium systems can be formulated in terms of dissipative, or irreversible, brackets. We discuss the structure of such irreversible brackets in view of a degeneracy implied by energy conservation, where we consider different types of symmetries of the bracket corresponding to the Onsager and Casimir symmetries of linear irreversible thermodynamics. Slip and turbulence provide important examples of antisymmetric irreversible brackets and offer guidance for the more general modeling of irreversible dynamics without entropy production. Conversely, turbulence modeling could benefit from elucidating thermodynamic structure. The examples suggest constructing antisymmetric irreversible brackets in terms of completely antisymmetric functions of three indices. Irreversible brackets without well-defined symmetry properties can arise for rare events, causing big configurational changes.

Nonequilibrium thermodynamics of the shear-transformation-zone model.

The shear-transformation-zone (STZ) model has been applied numerous times to describe the plastic deformation of different types of amorphous systems. We formulate this model within the general equation for nonequilibrium reversible-irreversible coupling (GENERIC) framework, thereby clarifying the thermodynamic structure of the constitutive equations and guaranteeing thermodynamic consistency. We propose natural, physically motivated forms for the building blocks of the GENERIC, which combine to produce a closed set of time evolution equations for the state variables, valid for any choice of free energy. We demonstrate an application of the new GENERIC-based model by choosing a simple form of the free energy. In addition, we present some numerical results and contrast those with the original STZ equations.

Nonlinear coupled equations for electrochemical cells as developed by the general equation for nonequilibrium reversible-irreversible coupling.

We show how the Butler-Volmer and Nernst equations, as well as Peltier effects, are contained in the general equation for nonequilibrium reversible and irreversible coupling, GENERIC, with a unique definition of the overpotential. Linear flux-force relations are used to describe the transport in the homogeneous parts of the electrochemical system. For the electrode interface, we choose nonlinear flux-force relationships. We give the general thermodynamic basis for an example cell with oxygen electrodes and electrolyte from the solid oxide fuel cell. In the example cell, there are two activated chemical steps coupled also to thermal driving forces at the surface. The equilibrium exchange current density obtains contributions from both rate-limiting steps. The measured overpotential is identified at constant temperature and stationary states, in terms of the difference in electrochemical potential of products and reactants. Away from these conditions, new terms appear. The accompanying energy flux out of the surface, as well as the heat generation at the surface are formulated, adding to the general thermodynamic basis.

Dynamics of multiphase systems with complex microstructure. I. Development of the governing equations through nonequilibrium thermodynamics.

In this paper we present a general model for the dynamic behavior of multiphase systems in which the bulk phases and interfaces have a complex microstructure (for example, immiscible polymer blends with added compatibilizers, or polymer stabilized emulsions with thickening agents dispersed in the continuous phase). The model is developed in the context of the GENERIC framework (general equation for the nonequilibrium reversible irreversible coupling). We incorporate scalar and tensorial structural variables in the set of independent bulk and surface excess variables, and these structural variables allow us to link the highly nonlinear rheological response typically observed in complex multiphase systems, directly to the time evolution of the microstructure of the bulk phases and phase interfaces. We present a general form of the Poisson and dissipative brackets for the chosen set of bulk and surface excess variables, and show that to satisfy the entropy degeneracy property, we need to add several contributions to the moving interface normal transfer term, involving the tensorial bulk and interfacial structural variables. We present the full set of balance equations, constitutive equations, and boundary conditions for the calculation of the time evolution of the bulk and interfacial variables, and this general set of equations can be used to develop specific models for a wide range of complex multiphase systems.

Deformation of inherent structures to detect long-range correlations in supercooled liquids.

We propose deformations of inherent structures as a suitable tool for detecting structural changes underlying the onset of cooperativity in supercooled liquids. The non-affine displacement (NAD) field resulting from the applied deformation shows characteristic differences between the high temperature liquid and supercooled state, which are typically observed in dynamic quantities. The average magnitude of the NAD is very sensitive to temperature changes in the supercooled regime and is found to be strongly correlated with the inherent structure energy. In addition, the NAD field is characterized by a correlation length that increases upon lowering the temperature towards the supercooled regime.

Probing a critical length scale at the glass transition.

We give evidence of a clear structural signature of the glass transition, in terms of a static correlation length with the same dependence on the system size, which is typical of critical phenomena. Our approach is to introduce an external, static perturbation to extract the structural information from the system's response. In particular, we consider the transformation behavior of the local minima of the underlying potential energy landscape (inherent structures), under a static deformation. The finite-size scaling analysis of our numerical results indicate that the correlation length diverges at a temperature Tc, below the temperatures where the system can be equilibrated. Our numerical results are consistent with random first order theory, which predicts such a divergence with a critical exponent ν=2/3 at the Kauzmann temperature, where the extrapolated configurational entropy vanishes.