Positive Entropy Production Research Articles

Stochastic Entropy Production Associated with Quantum Measurement in a Framework of Markovian Quantum State Diffusion

The reduced density matrix that characterises the state of an open quantum system is a projection from the full density matrix of the quantum system and its environment, and there are many full density matrices consistent with a given reduced version. Without a specification of relevant details of the environment, the time evolution of a reduced density matrix is therefore typically unpredictable, even if the dynamics of the full density matrix are deterministic. With this in mind, we investigate a two-level open quantum system using a framework of quantum state diffusion. We consider the pseudorandom evolution of its reduced density matrix when subjected to an environment-driven process that performs a continuous quantum measurement of a system observable, invoking dynamics that asymptotically send the system to one of the relevant eigenstates. The unpredictability is characterised by a stochastic entropy production, the average of which corresponds to an increase in the subjective uncertainty of the quantum state adopted by the system and environment, given the underspecified dynamics. This differs from a change in von Neumann entropy, and can continue indefinitely as the system is guided towards an eigenstate. As one would expect, the simultaneous measurement of two non-commuting observables within the same framework does not send the system to an eigenstate. Instead, the probability density function describing the reduced density matrix of the system becomes stationary over a continuum of pure states, a situation characterised by zero further stochastic entropy production. Transitions between such stationary states, brought about by changes in the relative strengths of the two measurement processes, give rise to finite positive mean stochastic entropy production. The framework investigated can offer useful perspectives on both the dynamics and irreversible thermodynamics of measurement in quantum systems.

Hybrid approach to perfect and dissipative spin hydrodynamics

A hybrid framework of spin hydrodynamics is proposed that combines the results of kinetic theory for particles with spin 1/2 with the Israel-Stewart method of introducing nonequilibrium dynamics. The framework of kinetic theory is used to define the perfect-fluid description that conserves baryon number, energy, linear momentum and spin part of angular momentum. This leads to the entropy conservation although, in the presence of spin degrees of freedom, the perfect-fluid formalism includes extra terms whose structure is usually attributed to dissipation. The genuine dissipative terms appear from the condition of positive entropy production in nonequilibrium processes. They are responsible for the transfer between the spin and orbital parts of angular momentum, with the total angular momentum being conserved. Published by the American Physical Society 2024

A comprehensive study on the roles of viscosity and heat conduction in shock waves

Shock waves are of great interest in many fields of science and engineering, but the mechanisms of their formation, maintenance and dissipation are still not well understood. While all transport processes existing in a shock wave contribute to its compression and irreversibility, they are not of equal importance. To figure out the roles of viscosity and heat conduction in shock transition, the existence of smooth shock solutions and the counter-intuitive entropy overshoot phenomenon (the specific entropy is not monotonically increasing and exhibits a peak inside the shock front) are theoretically and numerically investigated, with emphasis on the effects of viscosity and heat conduction. Instead of higher-order hydrodynamics, the Navier–Stokes formalism is employed for its stability and simplicity. Supplemented with nonlinear thermodynamically consistent constitutive relations, the Navier–Stokes equations are adequate to demonstrate the general nature of shock profiles. It is found that heat conduction cannot sustain strong shocks without the presence of viscosity, while viscosity can maintain smooth shock transition at all strengths, regardless of heat conduction. Hence, the critical role in shock compression is played by viscosity rather than heat conduction. Nevertheless, the dispensability of heat conduction would not compromise its essential role in the emergence of an entropy peak. It is the entropy flux resulting from heat conduction that neutralises the positive entropy production and thus prevents the decreasing entropy from violating the second law of thermodynamics. This mechanism of entropy overshoot has not been addressed previously in the literature and is revealed using the entropy balance equation.

Thermodynamically extended symplectic numerical simulation of viscoelastic, thermal expansion and heat conduction phenomena in solids

AbstractSymplectic numerical schemes for reversible dynamical systems predict the solution reliably over large times as well, and are a good starting point for extension to schemes for simulating irreversible situations like viscoelastic wave propagation and heat conduction coupled via thermal expansion occuring in rocks, plastics, biological samples etc. Dissipation error (artificial nonpreservation of energies and amplitudes) of the numerical solution should be as small as possible since it should not be confused with the real dissipation occurring in the irreversible system. In addition, the other well-known numerical artefact, dispersion error (artificial oscillations emerging at sharp changes), should also be minimal to avoid confusion with the true wavy behavior. The continuum thermodynamical aspects (respect for balances with fluxes, systematic constitutive relationships between intensive quantities and fluxes, the second law of thermodynamics with positive definite entropy production, and the spacetime-based kinematic viewpoint) prove valuable for obtaining such extended schemes and for monitoring the solutions. Generalizing earlier works in this direction, here, we establish and investigate such a numerical scheme for one-dimensional viscoelastic wave propagation in the presence of heat conduction coupled via thermal expansion, demonstrating long-term reliability and the applicability of thermodynamics-based quantities in supervising the quality of the solution.

(Poster Award Winner 2) Solvation Effects in Electrochemical Double Layers and Static Simulations

Batteries play a key role in future sustainable energy networks. Modelling these electro-chemical systems accurately provides a path to improved battery chemistries [1]. In recent years, research has identified highly concentrated electrolytes as promising constituents for battery cells with high energy density [2]. These are, however, complex systems, where the bulk electrolyte concentration and external electric potential significantly influences the electrochemical double layer (EDL) structure. It is challenging to model the behaviour of highly concentrated electrolytes near a charged surface.Here, we present a continuum transport theory for these materials, which incorporates solvation effects. The model is built up from the second law of thermodynamics by enforcing positive entropy production. By analysing contributions to entropy production, we can establish the free energy of the electrolyte system, which in turn constitutes the basic equations of the transport theory [3,4]. Our continuum model can describe both static and dynamic systems of highly concentrated electrolytes. To analyse the EDL, static simulations have proven effective due to their very low computation cost. Using this method, we are able to achieve concentration profiles at EDL length scales, when adding nonlocal contributions [4] even oscillatory behaviour can be recreated.Solvation is a key effect to consider when modelling reactions at the electrode surface or intercalation. The desolvation at the electrode surface constitutes an energy barrier, which must be overcome. Previous solvation models [5] use a static ion-solvent coordination number, therefore the stripping of the solvation shell in the double layer cannot be described. We address this concept by incorporating local solvation in our model, enabling a description of the electric forces desolvating ions in the EDL.Solvation is added to the free energy of the system by modifying the statistics which determine the entropic contribution. Additionally, we include a term to represent the ion-solvent interaction energy. Thus, two novel parameters are used to define the interaction – the maximum number of solvent molecules binding to a single ion, and the binding energy.We supplement our analytic discussion by numerical double layer simulations of an electrolyte consisting of an IL with a solvent, neutral or charged. Our results capture the relationship of ion-solvent binding energy and the desolvation potential. We can extract qualitative results down to a molecular scale from our model, allowing us to predict coarse grained behaviour of MD-simulations. By estimating the solvent coordination number at the electrode surface, it is possible to obtain a desolvation energy barrier.Figure: a ternary EDL for two different values of the binding energy, showing a nearly complete desolvation at the electrode for the smaller binding energyThis work was funded in the project POLiS by the Deutsche Forschungsgemeinschaft (DFG) under Germany´s Excellence Strategy – EXC 2154 – Project number 390874152.Literature: Armand, M.; Tarascon, J.-M. Nature 2008 451, 652.Giffin, G.A., Nat Commun 2022 13, 5250.Schammer, M. et al. J. Electrochem. Soc. 2021, 168, 026511.Schammer, M. et al. J. Phys. Chem. B2022, 126, 14, 2761–2776.Dreyer, W. et al. Electrochem. Comm. 2014, 43, 75-78. Figure 1

The irreversibility of relativistic time-dilation

The fluctuation relations, which characterize irreversible processes in nature, are among the most important results in non-equilibrium physics. In short, these relations say that it is exponentially unlikely for us to observe a time-reversed process and, thus, establish the thermodynamic arrow of time pointing from low to high entropy. On the other hand, fundamental physical theories are invariant under time-reversal symmetry. Although in Newtonian and quantum physics the emergence of irreversible processes, as well as fluctuation relations, is relatively well understood, many problems arise when relativity enters the game. In this work, by considering a specific class of spacetimes, we explore the question of how the time-dilation effect enters into the fluctuation relations. We conclude that a positive entropy production emerges as a consequence of both the special relativistic and the gravitational (enclosed in the equivalence principle) time-dilation effects.

Nonequilibrium thermodynamics of the asymmetric Sherrington-Kirkpatrick model

Most natural systems operate far from equilibrium, displaying time-asymmetric, irreversible dynamics characterized by a positive entropy production while exchanging energy and matter with the environment. Although stochastic thermodynamics underpins the irreversible dynamics of small systems, the nonequilibrium thermodynamics of larger, more complex systems remains unexplored. Here, we investigate the asymmetric Sherrington-Kirkpatrick model with synchronous and asynchronous updates as a prototypical example of large-scale nonequilibrium processes. Using a path integral method, we calculate a generating functional over trajectories, obtaining exact solutions of the order parameters, path entropy, and steady-state entropy production of infinitely large networks. Entropy production peaks at critical order-disorder phase transitions, but is significantly larger for quasi-deterministic disordered dynamics. Consequently, entropy production can increase under distinct scenarios, requiring multiple thermodynamic quantities to describe the system accurately. These results contribute to developing an exact analytical theory of the nonequilibrium thermodynamics of large-scale physical and biological systems and their phase transitions.

Revisit of Macroscopic Dynamics for Some Non-equilibrium Chemical Reactions from a Hamiltonian Viewpoint

Most biochemical reactions in living cells are open systems interacting with environment through chemostats to exchange both energy and materials. At a mesoscopic scale, the number of each species in those biochemical reactions can be modeled by a random time-changed Poisson processes. To characterize macroscopic behaviors in the large number limit, the law of large numbers in the path space determines a mean-field limit nonlinear reaction rate equation describing the dynamics of the concentration of species, while the WKB expansion for the chemical master equation yields a Hamilton–Jacobi equation and the Legendre transform of the corresponding Hamiltonian gives the good rate function (action functional) in the large deviation principle. In this paper, we decompose a general macroscopic reaction rate equation into a conservative part and a dissipative part in terms of the stationary solution to the Hamilton–Jacobi equation. This stationary solution is used to determine the energy landscape and thermodynamics for general chemical reactions, which particularly maintains a positive entropy production rate at a non-equilibrium steady state. The associated energy dissipation law at both the mesoscopic and macroscopic levels is proved together with a passage from the mesoscopic to macroscopic one. A non-convex energy landscape emerges from the convex mesoscopic relative entropy functional in the large number limit, which picks up the non-equilibrium features. The existence of this stationary solution is ensured by the optimal control representation at an undetermined time horizon for the weak KAM solution to the stationary Hamilton–Jacobi equation. Furthermore, we use a symmetric Hamiltonian to study a class of non-equilibrium enzyme reactions, which leads to nonconvex energy landscape due to flux grouping degeneracy and reduces the conservative–dissipative decomposition to an Onsager-type strong gradient flow. This symmetric Hamiltonian implies that the transition paths between multiple steady states (rare events in biochemical reactions) is a modified time reversed least action path with associated path affinities and energy barriers. We illustrate this idea through a bistable catalysis reaction and compute the energy barrier for the transition path connecting two steady states via its energy landscape.

Quantifying the Effects of Non‐Hydrostatic Stress on Multi‐Component Minerals

AbstractMineral compositions are used to infer pressures, temperatures, and timescales of geological processes. The thermodynamic techniques underlying these inferences assume a uniform, constant pressure. Nonetheless, convergent margins generate significant non‐hydrostatic (unequal) stresses, violating the uniform pressure assumption and creating uncertainty. Materials scientists F. Larché and J. Cahn derived an equation suitable for non‐hydrostatically stressed geologic environments that links stress and equilibrium composition in elastic, multi‐component crystals. However, previous works have shown that for binary solid solutions with ideal mixing behavior, hundreds of MPa to GPa‐level stresses are required to shift mineral compositions by a few hundredths of a mole fraction, limiting the equation's applicability. Here, we apply Larché and Cahn's equation to garnet, clinopyroxene, and plagioclase solid solutions, incorporating for the first time non‐ideal mixing behavior and more than two endmembers. We show that non‐ideal mixing increases predicted stress‐induced composition changes by up to an order of magnitude. Further, incorporating additional solid solution endmembers changes the predicted stress‐induced composition shifts of the other endmembers being considered. Finally, we demonstrate that Larché and Cahn's approach yields positive entropy production, a requirement for any real process to occur. Our findings reveal that stresses between tens and a few hundred MPa can shift mineral compositions by several hundredths of a mole fraction. Consequently, mineral compositions could plausibly be used to infer stress states. We suggest that stress‐composition effects could develop via intracrystalline diffusion in any high‐grade metamorphic setting, but are most likely in hot, dry, and strong rocks such as lower crustal granulites.

Gravitational entropy in Szekeres class I models

Developing a self-consistent notion of gravitational entropy in the context of cosmological structure formation has been so far an elusive task. Various theoretical proposals have been presented, initially based on Penrose’s Weyl curvature hypothesis, and variations of it. A more recent proposal by Clifton, Ellis, and Tavakol (CET) considered a novel approach by defining such entropy from a Gibbs equation constructed from an effective stress–energy tensor that emerges from the ‘square root’ algebraic decomposition of the Bel–Robinson tensor, the simplest divergence-less tensor related to the Weyl tensor. Since, so far all gravitational entropy proposals have been applied to highly restrictive and symmetric spacetimes, we probe in this paper the CET proposal for a class of much less idealized spacetimes (the Szekeres class I models) capable of describing the joint evolution of arrays of arbitrary number of structures: overdensities and voids, all placed on selected spatial locations in an asymptotic ΛCDM background. By using suitable covariant variables and their fluctuations, we find the necessary and sufficient conditions for a positive CET entropy production to be a negative sign of the product of the density and Hubble expansion fluctuations. To examine the viability of this theoretical result we examine numerically the CET entropy production for two elongated over dense regions surrounding a central spheroidal void, all evolving jointly from initial linear perturbations at the last scattering era into present day Mpc-size CDM structures. We show that CET entropy production is positive for all times after last scattering at the precise spatial locations where structure growth occurs and where the exact density growing mode is dominant. The present paper provides the least idealized (and most physically robust) probe of a gravitational entropy proposal in the context of structure formation.

Effect of sp3–sp2 Transformation on the Wear Rate of the DLC Coating

Based on the methods of non-equilibrium thermodynamics, it was found that the implementation of spontaneous processes with positive entropy production during friction leads to an increase in the wear intensity. Non-spontaneous processes with negative entropy production lead to a decrease in wear intensity. The tribological characteristics of diamond-like carbon (DLC) with different silicon content were studied. The wear intensity practically does not correlate with the friction coefficient. It is shown that DLC with the highest content of diamond-like inclusions (sp3) in the coating has the highest wear rate. In the same DLC, the most intense sp3–sp2 transformation during friction was observed. The sp3–sp2 transformation is a spontaneous process.

Relativistic hydrodynamics with the parity anomaly

We consider the hydrodynamic regime of a 2+1 dimensions QFT with the parity anomaly. Beyond the known constraints from positivity of entropy production, we show that the anomaly inflow mechanism, from a corresponding bulk SPT phase, together with thermodynamic consistency of equilibrium partition functions, restricts the form of non-dissipative transport coefficients. This included the known form of quantised Hall conductivity, which is fixed to be σxy = e2/2h, along with new constraints on other three non-dissipative parity-odd transport coefficients.

The positive entropy production property for augmented nonlinear hyperbolic models

Given a first-order nonlinear hyperbolic system of conservation laws endowed with a convex entropy-entropy flux pair, we consider the class of weak solutions containing shock waves depending upon some small scale parameters. In this Note, after introducing a notion of positive entropy production property that involves test-functions (rather than solutions), we define and derive several classes of entropy-dissipating augmented models, as we call them, which involve (possibly nonlinear) second- and third-order augmentation terms. Such terms typically arise in continuum physics and model viscosity and other high-order effects in a fluid. By introducing a new notion of positive entropy production that concerns general functions rather than solutions, we can easily check the entropy-dissipating property for a broad class of augmented models. The weak solutions associated with the corresponding zero-limit may contain (nonclassical undercompressive) shocks whose selection is determined from these high-order effects, for instance by using traveling wave solutions. Having a classification of the underlying models, as we propose, is essential for developing a general shock wave theory.

Scaling advantage of chaotic amplitude control for high-performance combinatorial optimization

The development of physical simulators, called Ising machines, that sample from low energy states of the Ising Hamiltonian has the potential to transform our ability to understand and control complex systems. However, most of the physical implementations of such machines have been based on a similar concept that is closely related to relaxational dynamics such as in simulated, mean-field, chaotic, and quantum annealing. Here we show that dynamics that includes a nonrelaxational component and is associated with a finite positive Gibbs entropy production rate can accelerate the sampling of low energy states compared to that of conventional methods. By implementing such dynamics on field programmable gate array, we show that the addition of nonrelaxational dynamics that we propose, called chaotic amplitude control, exhibits exponents of the scaling with problem size of the time to find optimal solutions and its variance that are smaller than those of relaxational schemes recently implemented on Ising machines.

The choice of a thermodynamic formulation dramatically affects modelled chemical zoning in minerals

Quantifying natural processes that shape our planet is a key to understanding the geological observations. Many phenomena in the Earth are not in thermodynamic equilibrium. Cooling of the Earth, mantle convection, mountain building are examples of dynamic processes that evolve in time and space and are driven by gradients. During those irreversible processes, entropy is produced. In petrology, several thermodynamic approaches have been suggested to quantify systems under chemical and mechanical gradients. Yet, their thermodynamic admissibility has not been investigated in detail. Here, we focus on a fundamental, though not yet unequivocally answered, question: which thermodynamic formulation for petrological systems under gradients is appropriate—mass or molar? We provide a comparison of both thermodynamic formulations for chemical diffusion flux, applying the positive entropy production principle as a necessary admissibility condition. Furthermore, we show that the inappropriate solution has dramatic consequences for understanding the key processes in petrology, such as chemical diffusion in the presence of pressure gradients.

Relativistic viscous effects on the primordial gravitational waves spectrum

We study the impact of the viscous effects of the primordial plasma on the evolution of the primordial gravitational waves (pGW) spectrum from Inflation until today, considering a self-consistent interaction that incorporates the back-reaction of the GW into the plasma. We use a relativistic causal hydrodynamic framework with a positive entropy production based on a Second-Order Theory (SOT) in which the viscous properties of the fluid are effectively described by a new set of independent variables. We study how the spin-2 modes typical of SOTs capture the simplest GW-fluid viscous interaction to first order. We consider that all non-ideal properties of the primordial plasma are due to an extra effectively massless self-interacting scalar field whose state becomes a many-particles one after Reheating and for which an effective fluid description is suitable. We numerically solve the evolution equations and explicitly compute the current GW spectrum obtaining two contributions. On the one hand we have the viscous evolution of the pGW: for the collision-dominated regime the GW source becomes negligible while in the collisionless limit there exists an absorption of the pGW energy due to the damping effect produced by the free-streaming spin-2 modes of the fluid and driven by the expansion of the Universe. The latter effect is characterized by a relative amplitude decrease of about 1 to 10 % with respect to the GW free evolution spectrum. On the other hand we get the GW production due to the decay of the initial spin-2 fluctuations of the fluid that is negligible compared with the above-mentioned contribution.This SOT framework captures the same qualitative effects on the evolution of GW coupled to matter reported in previous works in which a kinetic theory approach has been used.

Hierarchical-environment-assisted non-Markovian and its effect on thermodynamic properties

We consider a microscopic collision model, i.e., a quantum system interacts with a hierarchical environment consisting of an auxiliary system and a reservoir. We show how the non-Markovian character of the system is influenced by the coupling strength of system-auxiliary system and auxiliary system-reservoir, coherence of environment and initial system-environment correlations. And we study the non-Markovianity induced by coherence of environment from the perspective of energy, further the relationship between information backflow and energy flux is obtained. Then we study the effect of non-Markovianity on thermodynamic properties. By studying the entropy change of system especially that from heat exchanges with the environment, we reveal the essence of entropy change between positive and negative values during non-Markovian evolution is due to the contribution of heat flux induced by coherence. And compared with the case of Markovian dynamics, we observe that the entropy production decreases in some specific time intervals under non-Markovian dynamics induced by the coupling strength. And this is different to the case of non-Markovianity caused by initial system-environment correlation, that we show the possibility of positive entropy production during the whole dynamics.

Inherent Dissipation of Upwind‐Biased Potential Temperature Advection and its Feedback on Model Dynamics

AbstractHigher order upwind‐biased advection schemes are often used for potential temperature advection in dynamical cores of atmospheric models. The inherent diffusive and antidiffusive fluxes are interpreted here as the effect of irreversible sub‐gridscale dynamics. For those, total energy conservation and positive internal entropy production must be guaranteed. As a consequence of energy conservation, the pressure gradient term should be formulated in Exner pressure form. The presence of local antidiffusive fluxes in potential temperature advection schemes foils the validity of the second law of thermodynamics. Due to this failure, a spurious wind acceleration into the wrong direction is locally induced via the pressure gradient term. When correcting the advection scheme to be more entropically consistent, the spurious acceleration is avoided, but two side effects come to the fore: (i) the overall accuracy of the advection scheme decreases and (ii) the now purely diffusive fluxes become more discontinuous compared to the original ones, which leads to more sudden body forces in the momentum equation. Therefore, the amplitudes of excited gravity waves from jets and fronts increase compared to the original formulation with inherent local antidiffusive fluxes. The means used for supporting the argumentation line are theoretical arguments concerning total energy conservation and internal entropy production, pure advection tests, one‐dimensional advection‐dynamics interaction tests and evaluation of runs with a global atmospheric dry dynamical core.

Irreversible work and Maxwell demon in terms of quantum thermodynamic force

The second law of classical equilibrium thermodynamics, based on the positivity of entropy production, asserts that any process occurs only in a direction that some information may be lost (flow out of the system) due to the irreversibility inside the system. However, any thermodynamic system can exhibit fluctuations in which negative entropy production may be observed. In particular, in stochastic quantum processes due to quantum correlations and also memory effects we may see the reversal energy flow (heat flow from the cold system to the hot system) and the backflow of information into the system that leads to the negativity of the entropy production which is an apparent violation of the Second Law. In order to resolve this apparent violation, we will try to properly extend the Second Law to quantum processes by incorporating information explicitly into the Second Law. We will also provide a thermodynamic operational meaning for the flow and backflow of information. Finally, it is shown that negative and positive entropy production can be described by a quantum thermodynamic force.

First order non-Lorentzian fluids, entropy production, and linear instabilities

In this note, we investigate linear instabilities of hydrodynamics with corrections up to first order in derivatives. It has long been known that relativistic (Lorentzian) first order hydrodynamics, with positive local entropy production, exhibits unphysical instabilities. We extend this analysis to fluids with Galilean and Carrollian boost symmetries. We find that the instabilities occur in all cases, except for fluids with Galilean boost symmetry combined with the choice of macroscopic variables called Eckart frame. We also present a complete linearised analysis of the full spectrum of first order Carrollian hydrodynamics. Furthermore, we show that even in a fluid without boost symmetry present, instabilities can occur. These results provide evidence that the unphysical instabilities are symptoms of first order hydrodynamics, rather than a special feature of Lorentzian fluids.