Motility-induced phase separation (MIPS) arises generically in fluids of self-propelled particles when interactions lead to a kinetic slowdown at high densities. Starting from a continuum description of scalar active matter, akin to a generalized Cahn-Hilliard equation, we give a general prescription for the mean densities of coexisting phases in flux-free steady states that amounts, at a hydrodynamics scale, to extremizing an effective free energy. We illustrate our approach on two well-known models: self-propelled particles interacting either through a density-dependent propulsion speed or via direct pairwise forces. Our theory accounts quantitatively for their phase diagrams, providing a unified description of MIPS.
Motility-induced phase separation (MIPS) leads to cohesive active matter in the absence of cohesive forces. We present, extend and illustrate a recent generalized thermodynamic formalism which accounts for its binodal curve. Using this formalism, we identify both a generalized surface tension, that controls finite-size corrections to coexisting densities, and generalized forces, that can be used to construct new thermodynamic ensembles. Our framework is based on a nonequilibrium generalization of the Cahn-Hilliard equation and we discuss its application to active particles interacting either v…
We derive from first principles the mechanical pressure $P$, defined as the force per unit area on a bounding wall, in a system of spherical, overdamped, active Brownian particles at density $ρ$. Our exact result relates $P$, in closed form, to bulk correlators and shows that (i) $P(ρ)$ is a state function, independent of the particle-wall interaction; (ii) interactions contribute two terms to $P$, one encoding the slow-down that drives motility-induced phase separation, and the other a direct contribution well known for passive systems; (iii) $P(ρ)$ is equal in coexisting phases. We discuss t…
We present a unified approach to thermodynamic description of one, two and three dimensional phases and phase transformations among them. The approach is based on a rigorous definition of a phase applicable to thermodynamic systems of any dimensionality. Within this approach, the same thermodynamic formalism can be applied for the description of phase transformations in bulk systems, interfaces, and line defects separating interface phases. For both lines and interfaces, we rigorously derive an adsorption equation, the phase coexistence equations, and other thermodynamic relations expressed in…
This paper investigates applicability of thermodynamic concepts and principles to competitive systems. We show that Tsallis entropies are suitable for characterisation of systems with transitive competition when mutations deviate from Gibbs mutations. Different types of equilibrium in competitive systems are considered and analysed. As competition rules become more and more intransitive, thermodynamic analogies are eroded and the behaviour of the system can become complex. This work analyses the phenomenon of punctuated evolution in the context of the competitive risk/benefit dilemma.
A new type of phase separation in the polyelectrolyte solutions consisting of several types of charged macromolecules differing in their degree of ionization is predicted via a general thermodynamic consideration. We show that even a small difference in the degree of ionization of otherwise equivalent components results in their spatial separation occurring upon decreasing the temperature much earlier than precipitation of the components from the solution. Some implications of charge fractionation in biological processes are discussed.
A `polydisperse' system has an infinite number of conserved densities. We give a rational procedure for projecting its infinite-dimensional free energy surface onto a subspace comprising a finite number of linear combinations of densities (`moments'), in which the phase behavior is then found as usual. If the excess free energy of the system depends only on the moments used, exact cloud, shadow and spinodal curves result; two- and multi-phase regions are approximate, but refinable indefinitely by adding extra moments. The approach is computationally robust and gives new geometrical insights in…
The recently developed Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) is investigated for a wide range of model parameters including the parameter m representing the chain length and the thermodynamic temperature T and pressure p. This approach is based upon the first-order thermodynamic perturbation theory for chain molecules developed by Wertheim and Chapman et al. and includes dispersion interactions via the second-order perturbation theory of Barker and Henderson. We systematically study a hierarchy of models which are based on the PC-SAFT approach using analytical model ca…
The concept of weak invariants is examined in the thermodynamic context. Discussions are made about the temporally-local equilibrium states, corrections to them, and isoenergetic processes based on the quantum master equations of the Lindblad type that admit time-dependent Hamiltonians as weak invariants. The method for determining the correction presented here may be thought of as a quantum-mechanical analog of the Chapman-Enskog expansion in nonequilibrium classical statistical mechanics. Then, the theory is applied to the time-dependent harmonic oscillator as a simple example, and the power…
We determine the impact of the Friedel oscillations on the phase behavior, critical properties and thermodynamic contours in films ($2D$) and bulk phases ($3D$). Using Expanded Wang-Landau simulations, we calculate the grand-canonical partition function and, in turn, the thermodynamic properties of systems modeled with a linear combination of the Lennard-Jones and Dzugutov potentials, weighted by a parameter $X$ ($0<X<1$). Varying $X$ allows us to control the height of the first Friedel oscillation and to provide a complete characterization of the effect of the metal-like character in the pote…
Active systems evade the rules of equilibrium thermodynamics by constantly dissipating energy at the level of their microscopic components. This energy flux stems from the conversion of a fuel, present in the environment, into sustained individual motion. It can lead to collective effects without any equilibrium equivalent, such as a phase separation for purely repulsive particles, or a collective motion (flocking) for aligning particles. Some of these effects can be rationalized by using equilibrium tools to recapitulate nonequilibrium transitions. An important challenge is then to delineate …
The hallmark of active matter is the autonomous directed motion of its microscopic constituents driven by consumption of energy resources. This leads to the emergence of large scale dynamics and structures without any equilibrium equivalent. Though active field theories offer a useful hydrodynamic description, it is unclear how to properly quantify the energetic cost of the dynamics from such a coarse-grained description. We provide a thermodynamically consistent framework to identify the energy exchanges between active systems and their surrounding thermostat at the hydrodynamic level. Based …
The study of thermal heat engines was pivotal to establishing the principles of equilibrium thermodynamics, with implications far wider than only engine optimization. For nonequilibrium systems, which by definition dissipate energy even at rest, how to best convert such dissipation into useful work is still largely an outstanding question, with similar potential to illuminate general physical principles. We review recent theoretical progress in studying the performances of engines operating with active matter, where particles are driven by individual self-propulsion. We distinguish two main cl…
Active matter constantly dissipates energy to power the self-propulsion of its microscopic constituents. This opens the door to designing innovative cyclic engines without any equilibrium equivalent. We offer a consistent thermodynamic framework to characterize and optimize the performances of such cycles. Based on a minimal model, we put forward a protocol which extracts work by controlling only the properties of the confining walls at boundaries, and we rationalize the transitions between optimal cycles. We show that the corresponding power and efficiency are generally proportional, so that …
This article summarizes some of the open questions in the field of active matter that have emerged during Active20, a nine-week program held at the Kavli Institute for Theoretical Physics (KITP) in Spring 2020. The article does not provide a review of the field, but rather a personal view of the authors, informed by contributions of all participants, on new directions in active matter research. The topics highlighted include: the ubiquitous occurrence of spontaneous flows and active turbulence and the theoretical and experimental challenges associated with controlling and harnessing such flows…
We describe a technique for constraining macroscopic fluctuations in thermodynamic variables well-suited for Monte Carlo (MC) simulations of multiphase equilibria. In particular for multicomponent systems this amounts to a statistical ensemble that implements constraints on both the average composition as well as its fluctuations. The variance-constrained semi-grandcanonical (VC-SGC) ensemble allows for MC simulations, in which single-phase systems can be reversibly switched into multiphase equilibria allowing the calculation of excess free energies of precipitates of complex shapes by thermod…
Active biological systems reside far from equilibrium, dissipating heat even in their steady state, thus requiring an extension of conventional equilibrium thermodynamics and statistical mechanics. In this Letter, we have extended the emerging framework of stochastic thermodynamics to active matter. In particular, for the active Ornstein-Uhlenbeck model, we have provided consistent definitions of thermodynamic quantities such as work, energy, heat, entropy, and entropy production at the level of single, stochastic trajectories and derived related fluctuation relations. We have developed a gene…
Monte Carlo simulation provides a powerful tool for understanding and exploring thermodynamic phase equilibria in many-particle interacting systems. Among the most physically intuitive simulation methods is Gibbs ensemble Monte Carlo (GEMC), which allows direct computation of phase coexistence curves of model fluids by assigning each phase to its own simulation cell. When one or both of the phases can be modeled virtually via an analytic free energy function [M. Mehta and D. A. Kofke, Molecular Physics 79, 39 (1993)], the GEMC method takes on new pedagogical significance as an efficient means …
Thermodynamics of nanoscale devices is an active area of research. Despite their noisy surrounding they often produce mechanical work (e.g. micro-heat engines), display rectified Brownian motion (e.g. molecular motors). This invokes research in terms of experimentally quantifiable thermodynamic efficiencies. Here, a Brownian particle is driven by a harmonic confinement with time-periodic contraction and expansion. The system produces work by being alternately (time-periodically) connected to baths with different dissipations. We analyze the system theoretically using stochastic thermodynamics.…
A mean-field density-functional model for three-phase equilibria in fluids (or other soft condensed matter) with two spatially varying densities is analyzed analytically and numerically. The interfacial tension between any two out of three thermodynamically coexisting phases is found to be captured by a surprisingly simple analytic expression that has a geometric interpretation in the space of the two densities. The analytic expression is based on arguments involving symmetries and invariances. It is supported by numerical computations of high precision and it agrees with earlier conjectures o…
The Le Chatelier principle states that physical equilibria are not only stable, but they also resist external perturbations via short-time negative-feedback mechanisms: a perturbation induces processes tending to diminish its results. The principle has deep roots, e.g., in thermodynamics it is closely related to the second law and the positivity of the entropy production. Here we study the applicability of the Le Chatelier principle to evolutionary game theory, i.e., to perturbations of a Nash equilibrium within the replicator dynamics. We show that the principle can be reformulated as a major…
We recall the existing string theory understanding of black hole entropy and argue it is incomplete but we put forward a modified version, based on the author's 'matter-gravity entanglement hypothesis', which, we claim, gives a more satisfactory understanding and also a resolution to the Information Loss Puzzle. This hypothesis pictures a black hole equilibrium as an, overall pure, state, with given energy, consisting of a black hole with its (mostly matter) atmosphere in a box and identifies the black hole's entropy with the pure state's matter-gravity entanglement entropy. We assume this equ…
The relaxation of magnetically confined plasmas in a toroidal geometry is analyzed. From the equations for the Hermitian moments, we show how the system relaxes towards the mechanical equilibrium. In the space of the parallel generalized frictions, after fast transients, the evolution of collisional magnetically confined plasmas is such that the projections of the evolution equations for the parallel generalized frictions and the shortest path on the Hermitian moments coincide. For spatially-extended systems, a similar result is valid for the evolution of the {\it thermodynamic mode} (i.e., th…
From Action Principle to Stochastic Thermodynamics of Elastic and Viscous Active Matter
European Molecular Biology Laboratory（欧洲分子生物学实验室）；University of Turin（都灵大学）；Heidelberg University（海德堡大学）；University of Cambridge（剑桥大学）；Politecnico di Torino（都灵理工大学）；INFN, Sezione di Torino（意大利国家核物理研究所都灵分部）
Active matter is rapidly becoming a key paradigm of out-of-equilibrium soft matter exhibiting complex collective phenomena, yet the thermodynamics of such systems remain poorly understood. In this letter we study the nonequilbrium thermodynamics of large scale active systems capable of mobility-induced phase separation and polar alignment, using a fully under-damped model which exhibits hidden entropy productions not previously reported in the literature. We quantify steady state entropy production at each point in the phase diagram, revealing characteristic dissipation rates associated with t…
The theoretical understanding of active matter, which is driven out of equilibrium by directed motion, is still fragmental and model oriented. Stochastic thermodynamics, on the other hand, is a comprehensive theoretical framework for driven systems that allows to define fluctuating work and heat. We apply these definitions to active matter, assuming that dissipation can be modelled by effective non-conservative forces. We show that, through the work, conjugate extensive and intensive observables can be defined even in non-equilibrium steady states lacking a free energy. As an illustration, we …
Solid solutions, structurally ordered but compositionally disordered mixtures, can form for salts, metals, and even organic compounds. The NaCl-KCl system forms a solid solution at all compositions between 657°C and 505°C. Below a critical temperature of 505°C, the system exhibits a miscibility gap with coexisting Na-rich and K-rich rocksalt phases. We calculate the phase diagram in this region using the semi-grand canonical Widom method, which averages over virtual particle transmutations. We verify our results by comparison with free energies calculated from thermodynamic integration and ext…
We describe a self-contained procedure to evaluate the free energy of liquid and solid phases of an alloy system. The free energy of a single-element solid phase is calculated with thermodynamic integration using the Einstein crystal as the reference system. Then, free energy difference between the solid and liquid phases is calculated by Gibbs-Duhem integration. The central part of our method is the construction of a reversible alchemical path connecting a pure liquid and a liquid alloy to calculate the mixing enthalpy and entropy. We have applied the method to calculate the free energy of so…
From synthetic active devices such as self-propelling Janus colloids to micro-organisms like bacteria, micro-algae, living cells in tissues, active fluctuations are ubiquitous. Thermodynamics of small systems involving thermal as well as active fluctuations are of immense importance. They can be employed to extract thermodynamic work. Here we propose a simple model system that can produce thermodynamic work exploiting active fluctuations. We consider a Brownian particle, trapped by an externally controlled harmonic confinement which time-periodically contracts and expands by modulating its spr…
Sets of free energy differences are useful for finding the equilibria of chemical reactions, while absolute free energies have little physical meaning. However finding the relative free energy between two macrostates by subtraction of their absolute free energies is a valuable strategy in certain important cases. We present calculations of absolute free energies of biomolecules, using a combination of the well-known Einstein Molecule method (for treating the solute) with a conceptually related method of recent genesis for computing free energies of liquids (to treat the solvent and counterions…
Using an additivity property, we study particle-number fluctuations in a system of interacting self-propelled particles, called active Brownian particles (ABPs), which consists of repulsive disks with random self-propulsion velocities. From a fluctuation-response relation - a direct consequence of additivity, we formulate a thermodynamic theory which captures the previously observed features of nonequilibrium phase transition in the ABPs from a homogeneous fluid phase to an inhomogeneous phase of coexisting gas and liquid. We substantiate the predictions of additivity by analytically calculati…
Active matter, comprising many active agents interacting and moving in fluids or more complex environments, is a commonly occurring state of matter in biological and physical systems. By its very nature active matter systems exist in nonequilibrium states. In this paper the active agents are small Janus colloidal particles that use chemical energy provided by chemical reactions occurring on their surfaces for propulsion through a diffusiophoretic mechanism. As a result of interactions among these colloids, either directly or through fluid velocity and concentration fields, they may act collect…
Phase separation is the thermodynamic process that explains how droplets form in multicomponent fluids. These droplets can provide controlled compartments to localize chemical reactions, and reactions can also affect the droplets' dynamics. This review focuses on the tight interplay between phase separation and chemical reactions originating from thermodynamic constraints. In particular, simple mass action kinetics cannot describe chemical reactions since phase separation requires non-ideal fluids. Instead, thermodynamics implies that passive chemical reactions reduce the complexity of phase d…
Understanding stochastic thermodynamics of active Brownian particles (ABPs) system has been an important topic in very recent years. In this article we study a general model of active Brownian particle systems by introducing a coarse-grained Fokker-Planck equation, which allows us to identify an effective entropy production along a stochastic trajectory, wherein an activity and configuration dependent diffusion coefficient comes into play with an important role. Although the hidden component between the true entropy production and the effective one is dominant, the effective entropy production…
We demonstrate that the mechanically-defined "isothermal" compressibility behaves as a thermodynamic-like response function for suspensions of active Brownian particles. The compressibility computed from the active pressure - a combination of the collision and unique swim pressures - is capable of predicting the critical point for motility induced phase separation, as expected from the mechanical stability criterion. We relate this mechanical definition to the static structure factor via an active form of the thermodynamic compressibility equation and find the two to be equivalent, as would be…
We present a swarm model of Brownian particles with harmonic interactions, where the individuals undergo canonical active Brownian motion, i.e. each Brownian particle can convert internal energy to mechanical energy of motion. We assume the existence of a single global internal energy of the system. Numerical simulations show amorphous swarming behavior as well as static configurations. Analytic understanding of the system is provided by studying stability properties of equilibria.
Active matter has been intensely studied for its wealth of intriguing properties such as collective motion, motility-induced phase separation (MIPS), and giant fluctuations away from criticality. However, the precise connection of active materials with their equilibrium counterparts has remained unclear. For two-dimensional (2D) systems, this is also because the experimental and theoretical understanding of the liquid, hexatic, and solid equilibrium phases and their phase transitions is very recent. Here, we use self-propelled particles with inverse-power-law repulsions (but without alignment …
We describe the dynamics and thermodynamics of collisionless particle disks orbiting a massive central body, in the case where the disk mass is small compared to the central mass, the self-gravity of the disk dominates the non-Keplerian force, and the spread in semi-major axes is small. We show that with plausible approximations such disks have logarithmic two-body interactions and a compact phase space, and therefore exhibit thermodynamics that are simpler than most other gravitating systems, which require a confining box and artificial softening of the potential at small scales to be thermod…
Examples of self propulsion in strongly fluctuating environment is abound in nature, e.g., molecular motors and pumps operating in living cells. Starting from Langevin equation of motion, we develop a fluctuating thermodynamic description of self propelled particles using simple models of velocity dependent forces. We derive fluctuation theorems for entropy production and a modified fluctuation dissipation relation, characterizing the linear response at non-equilibrium steady states. We study these notions in a simple model of molecular motors, and in the Rayleigh-Helmholtz and energy-depot mo…
We perform an extensive analysis of passive as well as active micro-heat engines with different single-particle stochastic models. Using stochastic thermodynamics we calculate thermodynamic work, heat, entropy production and efficiency of passive and active Brownian heat engines analytically as well as numerically and compare them. We run the heat engines with a protocol for which the average thermodynamic quantities are calculated exactly for an arbitrary cycle time. We also discuss about the group of protocols for which exact non-quasistatic calculations can be done, completely in the passiv…
At thermal equilibrium, intensive quantities like temperature and pressure have to be uniform throughout the system, restricting inhomogeneous systems composed of different phases. The paradigmatic example is the coexistence of vapor and liquid, a state that can also be observed for active Brownian particles steadily driven away from equilibrium. Recently, a strategy has been proposed that allows to predict phase equilibria of active particles [Phys. Rev. E \textbf{97}, 020602(R)(2018)]. Here we elaborate on this strategy and formulate it in the framework of a van der Waals theory for active d…
Optimal active engines obey the thermodynamic Lorentz force law
NSF-Simons National Institute for Theory and Mathematics in Biology（NSF-西蒙斯生物理论与数学国家研究所）；Department of Physics, University of California, Berkeley（加州大学伯克利分校物理系）；Redwood Center For Theoretical Neuroscience, University of California, Berkeley（加州大学伯克利分校红woods理论神经科学中心）；Department of Physics and Astronomy and the Center for Soft and Living Matter, University of Pennsylvania（宾夕法尼亚大学天体物理学与天文学系及软物质与生命物质中心）；Department of Neuroscience, University of California, Berkeley（加州大学伯克利分校神经科学系）
The two classes of membrane transport, namely, secondary active and passive transport, are understood as different reaction pathways in the same protein structure, described by the 16-state model in this paper. To quantify the thermodynamic difference between secondary active transport and passive transport, we extend the second law of information thermodynamics of the autonomous demon in the four-state model composed of two subsystems to the 16-state model composed of four subsystems representing the membrane transport. We reduce the 16 states to 4 states and derive the coarse-grained second …
