A deterministic theory describing the behavior of an ultrathin lubricant film between two atomically-smooth solid surfaces is proposed. For the description of lubricant state the parameter of excess volume arising due to chaotization of solid medium structure in the course of melting is introduced. Thermodynamic and shear melting is described consistently. Dependences of friction force on temperature of lubricant, shear velocity of rubbing surfaces, and pressure upon surfaces are analyzed. Within the framework of a simple tribological model the stick-slip mode of friction, when the lubricant periodically melts and solidifies, is described. The obtained results are qualitatively compared with the experimental data.
Developing the non-equilibrium thermodynamics of friction is required for systematic design of low friction surfaces for a broad range of technological applications. Intuitively, the thermodynamic work done by a material sliding along a surface is expected to be partially dissipated as heat and partially transformed into the change of the internal energy of the system. However, general non-equilibrium thermodynamic principles governing this separation are presently unknown. We develop a theoretical framework based on the transition state theory combined with the conventional Prandtl-Tomlinson …
The melting of ultrathin lubricant film is studied by friction between atomically flat surfaces. The fluctuations of lubricant temperature are taken into account defined by Ornstein-Uhlenbeck process. The phase diagrams and portraits are calculated for the cases of second-order and first-order transitions -- the melting of amorphous and crystalline lubricants. It is shown that in the first case the stick-slip friction domain appears, dividing the regions of dry and sliding friction. In the second case the three stick-slip friction domains arise characterized by transitions between dry, metasta…
We investigate a mechanism of the appearance of kinetic friction in granular materials. We consider a small number of intervening inelastic particles between two rough surfaces as one of the simplest dynamical models to study granular friction. The resistance force applied to the upper surface is numerically calculated. We find that the resistance force F(t) is scaled as F'(vt) for a small pulling velocity v. The time average F_0=<F(t)> in the limit v->0 is not zero owing to the mutual collisions between the intervening particles. The nonzero F_0 implies the appearance of kinetic friction in t…
We investigate the velocity dependence of kinetic friction with a model which makes minimal assumptions on the actual mechanism of friction so that it can be applied at many scales provided the system involves multi-contact friction. Using a recently developed master equation approach we investigate the influence of two concurrent processes. First, at a nonzero temperature thermal fluctuations allow an activated breaking of contacts which are still below the threshold. As a result, the friction force monotonically increases with velocity. Second, the aging of contacts leads to a decrease of th…
The contribution of sliding-induced, atomic-scale instabilities to the kinetic friction force is investigated by molecular dynamics. For this purpose, we derive a relationship between the kinetic friction force $F_{\rm k}$ and the non-equilibrium velocity distribution $P(v)$ of the lubricant particles. $P(v)$ typically shows exponential tails, which cannot be described in terms of an effective temperature. It is investigated which parameters control the existence of instabilities and how they affect $P(v)$ and hence $F_{\rm k}$. The effects of the interfaces' dimensionality, lubricant coverage…
Within the framework of a Boltzmann-Lorentz equation, we analyze the dynamics of a granular rotor immersed in a bath of thermalized particles in the presence of a frictional torque on the axis. In numerical simulations of the equation, we observe two scaling regimes at low and high bath temperatures. In the large friction limit, we obtain the exact solution of a model corresponding to asymptotic behavior of the Boltzmann-Lorentz equation. In the limit of large rotor mass and small friction, we derive a Fokker-Planck equation for which the exact solution is also obtained.
Based on the trajectories of the separation between water molecule pairs from MD simulations, we investigate the bond breakage dynamics in bulk water. From the spectrum of mean first-passage times, the Fokker-Planck equation allows us to derive the diffusivity profile along the separation coordinate and thus to unambiguously disentangle the effects of free-energy and local friction on the separation kinetics. For tightly coordinated water the friction is six times higher than in bulk, which can be interpreted in terms of a dominant reaction path that involves additional orthogonal coordinates.
We consider a spring-block model with both dry and viscous frictions, subjected to a periodic driving allowing mechanically stable configurations to be sampled. We show that under strong driving, the scaling of the correlation length with the energy density is incompatible with the prediction of Edwards statistical approach, which assumes a uniform sampling of mechanically stable configurations. A crossover between the Edwards scaling and the non-standard high energy scaling is observed at energy scales that depend on the viscous friction coefficient. Generalizing Edwards thermodynamics, we pr…
We obtain, using semi-analytical transfer operator techniques, the Edwards thermodynamics of a one-dimensional model of blocks connected by harmonic springs and subjected to dry friction. The theory is able to reproduce the linear divergence of the correlation length as a function of energy density observed in direct numerical simulations of the model under tapping dynamics. We further characterize analytically this divergence using a Gaussian approximation for the distribution of mechanically stable configurations, and show that it is related to the existence of a peculiar infinite temperatur…
We discuss the thermodynamics of closed quantum systems driven out of equilibrium by a change in a control parameter and undergoing a unitary process. We compare the work actually done on the system with the one that would be performed along ideal adiabatic and isothermal transformations. The comparison with the latter leads to the introduction of irreversible work, while that with the former leads to the introduction of inner friction. We show that these two quantities can be treated on equal footing, as both can be linked with the heat exchanged in thermalization processes and both can be ex…
We present first elements of kinetic theory appropriate to the inhomogeneous phase of the HMF model. In particular, we investigate the case of strongly inhomogeneous distributions for $T\to 0$ and exhibit curious behaviour of the force auto-correlation function and friction coefficient. The temporal correlation function of the force has an oscillatory behaviour which averages to zero over a period. By contrast, the effects of friction accumulate with time and the friction coefficient does not satisfy the Einstein relation. On the contrary, it presents the peculiarity to increase linearly with …
A tribological system consisting of two contacting blocks has been considered. One of them is arranged between two springs, the other is driven periodically. The kinetics of the system has been studied in the boundary friction mode, when an ultrathin lubricant film is contained between the atomically smooth surfaces. In order to describe the film state, the expression for the free energy density is used in the form of an expansion in a power series in the order parameter, the latter being reduced to the shear modulus of a lubricant. The stick-slip mode is shown to be realized in a wide range o…
We perform large-scale molecular dynamics simulations to study heated granular fluids in three dimensions. Granular particles dissipate their kinetic energy due to solid frictional interaction with other particles. The velocity of each particle is perturbed by a uniformly-distributed random noise, which mimics the heating. At the early stage of evolution, the kinetic energy of the system decays with time and reaches a steady state at a later stage. The velocity distribution in the steady state shows a non-Gaussian distribution. This has been characterized by using the Sonine polynomial expansi…
How much free energy is irreversibly lost during a thermodynamic process? For deterministic protocols, lower bounds on energy dissipation arise from the thermodynamic friction associated with pushing a system out of equilibrium in finite time. Recent work has also bounded the cost of precisely moving a single degree of freedom. Using stochastic thermodynamics, we compute the total energy cost of an autonomously controlled system by considering both thermodynamic friction and the entropic cost of precisely directing a single control parameter. Our result suggests a challenge to the usual unders…
The decomposition kinetics of a solid-solution into separate phases are analyzed with an equation of motion initially developed to account for dissipative processes in quantum systems. This equation and the steepest-entropy-ascent quantum thermodynamic framework of which it is a part make it possible to track kinetic processes in systems in non-equilibrium, while retaining the framework of classical equilibrium thermodynamics. The general equation of motion is particularized for the case of the decomposition of a binary alloy, and a solution model is used to build an approximate energy eigenst…
Stochastic thermodynamics is formulated for variables that are odd under time reversal. The invariance under spatial rotation of the collision rates due to the isotropy of the heat bath is shown to be a crucial ingredient. An alternative detailed fluctuation theorem is derived, expressed solely in terms of forward statistics. It is illustrated for a linear kinetic equation with kangaroo rates.
We review and complete the existing literature on the kinetic theory of spatially homogeneous systems with long-range interactions taking collective effects into account. The evolution of the system as a whole is described by the Lenard-Balescu equation which is valid in a weak coupling approximation. When collective effects are neglected it reduces to the Landau equation and when collisions (correlations) are neglected it reduces to the Vlasov equation. The relaxation of a test particle in a bath is described by a Fokker-Planck equation involving a diffusion term and a friction term. For a th…
In the complete system of equations of evolution of the classical system of charges and the electromagnetic field generated by them, the field variables are excluded. An exact closed relativistic non-Hamiltonian system of nonlocal kinetic equations, that describes the evolution of a system of charges in terms of their microscopic distribution functions, is obtained . The solutions of this system of equations are non-invariant with respect to time reversal, and also have the property of hereditarity.
In this chapter, we illustrate recently obtained thermodynamic bounds for a number of enzymatic networks by focusing on simple examples of unicyclic or multi-cyclic networks. We also derive complementary relations which constrain the fluctuations of first-passage times to reach a threshold current.
Understanding current fluctuations is of fundamental importance and paves the way for the development of practical applications. According to the thermodynamic and kinetic uncertainty relations, the precision of currents can be constrained solely by total entropy production or dynamical activity. In this study, we derive a tighter bound on the precision of currents in terms of both thermodynamic and kinetic quantities, demonstrating that these quantities jointly constrain current fluctuations. The thermodynamic and kinetic uncertainty relations become particular cases of our result in asymptot…
A dilute gas of particles with short range interactions is considered in a shearing stationary state. A Gaussian thermostat keeps the total kinetic energy constant. For infinitely many particles it is shown that the thermostat becomes a friction force with constant friction coefficient. For finite number of particles N, the fluctuations around this constant are of order one over the square root of N, and distributed approximately Gaussian with deviations for large fluctuations. These deviations prohibit a derivation of fluctuation-dissipation relations far from equilibrium, based on the Fluctu…
We propose a formal extension of thermodynamics and kinetic theories to a larger class of entropy functionals. Kinetic equations associated to Boltzmann, Fermi, Bose and Tsallis entropies are recovered as a special case. This formalism first provides a unifying description of classical and quantum kinetic theories. On the other hand, a generalized thermodynamical framework is justified to describe complex systems exhibiting anomalous diffusion. Finally, a notion of generalized thermodynamics emerges in the context of the the violent relaxation of collisionless stellar systems and two-dimension…
We introduce a new class of nonlocal kinetic equations and nonlocal Fokker-Planck equations associated with an effective generalized thermodynamical formalism. These equations have a rich physical and mathematical structure that can describe phase transitions and blow-up phenomena. On general grounds, our formalism can have applications in different domains of physics, astrophysics, hydrodynamics and biology. We find an aesthetic connexion between topics (stars, vortices, bacteries,...) which were previously disconnected. The common point between these systems is the (attractive) long-range na…
An exact closed relativistic kinetic equation is derived for a system of identical classical particles interacting with each other through a scalar field. The microscopic deterministic mechanism of the irreversible equilibration process in a relativistic classical system of interacting particles has been established. Keywords: Irreversible equilibration process; Classical relativistic dynamics; Retarded interactions.
A covariant Fokker-Planck type equation for a simple gas and an equation for the Brownian motion are derived from a relativistic kinetic theory based on the Boltzmann equation. For the simple gas the dynamic friction four-vector and the diffusion tensor are identified and written in terms of integrals which take into account the collision processes. In the case of Brownian motion, the Brownian particles are considered as non-relativistic whereas the background gas behaves as a relativistic gas. A general expression for the semi-relativistic viscous friction coefficient is obtained and the part…
Redfield theory provides a closed kinetic description of a quantum system in weak contact with a very dense reservoir. Landau-Zener theory does the same for a time-dependent driven system in contact with a sparse reservoir. Using a simple model, we analyze the validity of these two theories by comparing their predictions with exact numerical results. We show that despite their a priori different range of validity, these two descriptions can give rise to an identical quantum master equation. Both theories can be used for a nonequilibrium thermodynamic description which we show is consistent wit…
We use mesoscopic non-equilibrium thermodynamics theory to describe RNA unfolding under tension. The theory introduces reaction coordinates, characterizing a continuum of states for each bond in the molecule. The unfolding considered is so slow that one can assume local equilibrium in the space of the reaction coordinates. In the quasi-stationary limit of high sequential barriers, our theory yields the master equation of a recently proposed sequential-step model. Non-linear switching kinetics is found between open and closed states. Our theory unifies the thermodynamic and kinetic descriptions…
We explore the thermodynamic geometry of a simple system that models the bistable dynamics of nucleic acid hairpins in single molecule force-extension experiments. Near equilibrium, optimal (minimum-dissipation) driving protocols are governed by a generalized linear response friction coefficient. Our analysis and simulations demonstrate that the friction coefficient of the driving protocols is sharply peaked at the interface between metastable regions, which leads to minimum-dissipation protocols that drive rapidly within a metastable basin, but then linger longest at the interface, giving the…
We briefly review the recently developed, Markov process based isothermal chemical thermodynamics for nonlinear, driven mesoscopic kinetic systems. Both the instantaneous Shannon entropy {\boldmath $S[p_α(t)]$} and relative entropy {\boldmath $F[p_α(t)]$}, defined based on probability distribution {\boldmath $\{p_α(t)\}$}, play prominent roles. The theory is general; and as a special case when a chemical reaction system is situated in an equilibrium environment, it agrees perfectly with Gibbsian chemical thermodynamics: {\boldmath $k_BS$} and {\boldmath $k_BTF$} become thermodynamic entropy an…
We report a theoretical study of stochastic processes modeling the growth of first-order Markov copolymers, as well as the reversed reaction of depolymerization. These processes are ruled by kinetic equations describing both the attachment and detachment of monomers. Exact solutions are obtained for these kinetic equations in the steady regimes of multicomponent copolymerization and depolymerization. Thermodynamic equilibrium is identified as the state at which the growth velocity is vanishing on average and where detailed balance is satisfied. Away from equilibrium, the analytical expression …
A nonequilibrium thermodynamic theory demonstrating an induction effect of a statistical nature is presented. We have shown that this thermodynamic induction can arise in a class of systems that have variable kinetic coefficients (VKC). In particular if a kinetic coefficient associated with a given thermodynamic variable depends on another thermodynamic variable then we have derived an expression that can predict the extent of the induction. The amount of induction is shown to be proportional to the square of the driving force. The nature of the intervariable coupling for the induction effect …
In this work we present a formalism to describe non equilibrium conditions in systems with a discretized energy spectrum, such as quantum systems. We develop a formalism based on a combination of Gibbs-Shannon entropy and information thermodynamics that arrives to a generalization of the De-Brujin identity applicable to discrete and non-symmetric distributions. This allows to define the concept of a thermodynamic temperature with a different, albeit complementary meaning to the equilibrium kinetic temperature of a system. The theory is applied to Bosonic and Fermionic cases represented by an h…
We show that a nominal temperature can be consistently and uniquely defined everywhere in the phase diagram of large classes of nonequilibrium kinetic Ising spin models. In addition, we confirm the recent proposal that, at critical points, the large-time ``fluctuation-dissipation ratio'' $X_\infty$ is a universal amplitude ratio and find in particular $X_\infty \approx 0.33(2)$ and $X_\infty = 1/2$ for the magnetization in, respectively, the two-dimensional Ising and voter universality classes.
Motivated by a recent work on the metabolism of carbohydrates in bacteria, we study the kinetics and thermodynamics of two classic models for reversible polymerization, one preserving the total polymer concentration and the other one not. The chemical kinetics is described by rate equations following the mass-action law. We consider a closed system and nonequilibrium initial conditions and show that the system dynamically evolves towards equilibrium where detailed balance is satisfied. The entropy production during this process can be expressed as the time derivative of a Lyapunov function. Wh…
We introduce a fractional Fokker-Planck equation (FFPE) for Levy flights in the presence of an external field. The equation is derived within the framework of the subordination of random processes which leads to Levy flights. It is shown that the coexistence of anomalous transport and a potential displays a regular exponential relaxation towards the Boltzmann equilibrium distribution. The properties of the Levy-flight FFPE derived here are compared with earlier findings for subdiffusive FFPE. The latter is characterized by a non-exponential Mittag-Leffler relaxation to the Boltzmann distributi…
Kinetics of steady-state copolymerization has been investigated since 1940s. Irreversible terminal and penultimate models were successfully applied to a number of comonomer systems, but failed for systems where depropagation is significant. Although a general mathematical treatment of the terminal model with depropagation was established in 1980s, penultimate model and higher-order terminal models with depropagation have not been systematically studied, since depropagation leads to hierarchically-coupled and unclosed kinetic equations which are hard to be solved analytically. In this work, we …
This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with $N$ species, $M$ reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemistry kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy functi…
The high accuracy exhibited by biological information transcription processes is due to kinetic proofreading, i.e., by a mechanism which reduces the error rate of the information-handling process by driving it out of equilibrium. We provide a consistent thermodynamic description of enzyme-assisted assembly processes involving competing substrates, in a Master Equation framework. We introduce and evaluate a measure of the efficiency based on rigorous non-equilibrium inequalities. The performance of several proofreading models are thus analyzed and the related time, dissipation and efficiency vs…
