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 collectively to form structures such as dynamic clusters. A general nonequilibrium thermodynamics framework for the description of such systems is presented that accounts for both self-diffusiophoresis and diffusiophoresis due to external concentration gradients, and is consistent with microreversibility. It predicts the existence of a reciprocal effect of diffusiophoresis back onto the reaction rate for the entire collection of colloids in the system, as well as the existence of a clustering instability that leads to nonequilibrium inhomogeneous system states.
Nonequilibrium interfacial thermodynamics is formulated in the presence of surface reactions for the study of diffusiophoresis in isothermal systems. As a consequence of microreversibility and Onsager-Casimir reciprocal relations, diffusiophoresis, i.e., the coupling of the tangential components of the pressure tensor to the concentration gradients of solute species, has a reciprocal effect where the interfacial currents of solutes is coupled to the slip velocity. The presence of surface reactions is shown to modify the diffusiophoretic and reciprocal effects at the fluid-solid interface. The …
The propulsion of active particles by self-diffusiophoresis is driven by asymmetric catalytic reactions on the particle surface that generate a mechanochemical coupling between the fluid velocity and the concentration fields of fuel and product in the surrounding solution. Because of thermal and molecular fluctuations in the solution, the motion of micrometric or submicrometric active particles is stochastic. Coupled Langevin equations describing the translation, rotation, and reaction of such active particles are deduced from fluctuating chemohydrodynamics and fluctuating boundary conditions …
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…
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…
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 v…
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.…
Recent experiments on active materials, such as dense bacterial suspensions and microtubule-kinesin motor mixtures, show a promising potential for achieving self-sustained flows. However, to develop active microfluidics it is necessary to understand the behaviour of active systems confined to channels. Therefore here we use continuum simulations to investigate the behaviour of active fluids in a two-dimensional channel. Motivated by the fact that most experimental systems show no ordering in the absence of activity, we concentrate on temperatures where there is no nematic order in the passive …
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…
We introduce a closure model for coarse-grained kinetic theories of polar active fluids. Based on a quasi-equilibrium approximation of the particle distribution function, the model closely captures important analytical properties of the kinetic theory, including its linear stability and the balance of entropy production and dissipation. Nonlinear simulations show the model reproduces the qualitative behavior and nonequilibrium statistics of the kinetic theory, unlike commonly used closure models. We use the closure model to simulate highly turbulent suspensions in both two and three dimensions…
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…
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）
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…
Nonequilibrium energetics of sensing and actuation by a smart active particle
University of Cambridge（剑桥大学）；Max Planck Institute for Dynamics and Self-Organization (MPIDS)（马克斯·普朗克动力学与自组织研究所）；University of Rome “Tor Vergata”（罗马托维尔加塔大学）
Optimisation of heat engines at the micro-scale has applications in biological and artificial nano-technology, and stimulates theoretical research in non-equilibrium statistical physics. Here we consider non-interacting overdamped particles confined by an external harmonic potential, in contact either with a thermal reservoir or with a stochastic self-propulsion force (active Ornstein-Uhlenbeck model). A cyclical machine is produced by periodic variation of the parameters of the potential and of the noise. An exact mapping between the passive and the active model allows us to define the effect…
Onsager's variational principle (OVP) was originally proposed by Lars Onsager in 1931 [L. Onsager, $Phys. Rev.$, 1931, $37$, 405]. This fundamental principle provides a very powerful tool for formulating thermodynamically consistent models. It can also be employed to find approximate solutions, especially in the study of soft matter dynamics. In this work, OVP is extended and applied to the dynamic modeling of active soft matter such as suspensions of bacteria and aggregates of animal cells. We first extend the general formulation of OVP to active matter dynamics where active forces are includ…
In contrast with a gas at thermodynamic equilibrium, the mean force exerted on a wall by a gas of active particles usually depends on the confining potential, thereby preventing a proper definition of mechanical pressure. In this paper, we investigate numerically the properties of a gas of underdamped self-propelled dumbbells subject to Brownian noise of increasing intensity, in order to understand how the notion of pressure is recovered as noise progressively masks the effects of self-propulsion and the system approaches thermodynamic equilibrium. The simulations performed for a mobile asymme…
Demixing of binary liquids is a ubiquitous transition, which is explained using a well-established thermodynamic formalism that requires equality of intensive thermodynamics parameters across the phase boundaries. Demixing transitions also occur when binary fluid mixtures are driven away from equilibrium, for example, by external shear flow. Predicting demixing transition under non-equilibrium non-potential conditions remains, however, a challenge. We drive liquid-liquid phase separation (LLPS) of attractive DNA nanostar molecules away from equilibrium using an internally driven microtubule-ba…
We utilize a generalized Irving-Kirkwood procedure to derive the hydrodynamic equations of an active matter suspension with internal structure and driven by internal torque. The internal structure and torque of the active Brownian particles give rise to a balance law for internal angular momentum density, making the hydrodynamic description a polar theory of continuum mechanics. We derive exact microscopic expressions for the stress tensor, couple stress tensor, internal energy density, and heat flux vector. Unlike passive matter, the symmetry of the stress tensor is broken explicitly due to a…
Pressure is the mechanical force per unit area that a confined system exerts on its container. In thermal equilibrium, it depends only on bulk properties (density, temperature, etc.) through an equation of state. Here we show that in a wide class of active systems the pressure depends on the precise interactions between the active particles and the confining walls. In general, therefore, active fluids have no equation of state, their mechanical pressures exhibit anomalous properties that defy the familiar thermodynamic reasoning that holds in equilibrium. The pressure remains a function of sta…
Active matter systems are inherently out of equilibrium and break the detailed balance (DB) at the microscopic scale, exhibiting vital collective phenomena such as motility-induced phase separation (MIPS). Here, we introduce a coarse-grained mapping method to probe DB breaking in the density-energy phase space, which allows us to reveal the dynamic and thermodynamic origins of MIPS based on nonequilibrium potential and flux landscape theory. Hallmarks of nonequilibrium properties are manifested by identifying the visible probability flux in the coarse-grained phase space. Remarkably, the flux …
Collections of self-propelled particles that move persistently by continuously consuming free energy are a paradigmatic example of active matter. In these systems, unlike Brownian "hot colloids", the breakdown of detailed balance yields a continuous production of entropy at steady state, even for an ideal active gas. We quantify the irreversibility for a non-interacting active particle in two dimensions by treating both conjugated and time-reversed dynamics. By starting with underdamped dynamics, we identify a hidden rate of entropy production required to maintain persistence and prevent the r…
We study microscopic engines that use a single active particle as their "working medium". Part of the energy required to drive the directed motion of the particle can be recovered as work, even at constant temperature. A wide class of synthetic active particles can be captured by schematically accounting for the chemical degrees of freedom that power the directed motion without having to resolve the exact microscopic mechanism. We derive analytical results for the quasi-static thermodynamic efficiency, i.e., the fraction of available chemical energy that can be recovered as mechanical work. Wh…
Field theories for the one-body density of an active fluid, such as the paradigmatic active model B+, are simple yet very powerful tools for describing phenomena such as motility-induced phase separation. No comparable theory has been derived yet for the underdamped case. In this work, we introduce active model I+, an extension of active model B+ to particles with inertia. The governing equations of active model I+ are systematically derived from the microscopic Langevin equations. We show that, for underdamped active particles, thermodynamic and mechanical definitions of the velocity field no…
We review the state of the art of active fluids with particular attention to hydrodynamic continuous models and to the use of Lattice Boltzmann Methods (LBM) in this field. We present the thermodynamics of active fluids, in terms of liquid crystals modelling adapted to describe large-scale organization of active systems, as well as other effective phenomenological models. We discuss how LBM can be implemented to solve the hydrodynamics of active matter, starting from the case of a simple fluid, for which we explicitly recover the continuous equations by means of Chapman-Enskog expansion. Going…
Binary fluid mixtures are examples of complex fluids whose microstructure and flow are strongly coupled. For pairs of simple fluids, the microstructure consists of droplets or bicontinuous demixed domains and the physics is controlled by the interfaces between these domains. At continuum level, the structure is defined by a composition field whose gradients which are steep near interfaces drive its diffusive current. These gradients also cause thermodynamic stresses which can drive fluid flow. Fluid flow in turn advects the composition field, while thermal noise creates additional random fluxe…
