arXiv subjects

Pierre Illien

Publications and source records attributed to Pierre Illien.

At least 37 records · Page 2Linked to original sources

arXiv2023

On analytical theories for conductivity and self-diffusion in concentrated electrolytes

Describing analytically the transport properties of electrolytes, such as their conductivity or the self-diffusion of the ions, has been a central challenge of chemical physics for almost a century. In recent years, this question has regained some interest in light of Stochastic Density Field Theory (SDFT) -- an analytical framework that allows the approximate determination of density correlations in fluctuating systems. In spite of the success of this theory to describe dilute electrolytes, its extension to concentrated solutions raises a number of technical difficulties, and requires simplified descriptions of the short-range repulsion between the ions. In this article, we discuss recent approximations that were proposed to compute the conductivity of electrolytes, in particular truncations of Coulomb interactions at short distances. We extend them to another observable (the self-diffusion coefficient of the ions) and compare them to earlier analytical approaches, such as the mean spherical approximation and mode-coupling theory. We show how the treatment of hydrodynamic effects in SDFT can be improved, that the choice of the modified Coulomb interactions significantly affects the determination of the properties of the electrolytes, and that comparison with other theories provides a guide to extend SDFT approaches in this context.

cond-mat.soft↗

arXiv2023

Isotropic active colloids: explicit vs. implicit descriptions of propulsion mechanisms

Modeling the couplings between active particles often neglects the possible many-body effects that control the propulsion mechanism. Accounting for such effects requires the explicit modeling of the molecular details at the origin of activity. Here, we take advantage of a recent two-dimensional model of isotropic active particles whose propulsion originates from the interactions between solute particles in the bath. The colloid catalyzes a chemical reaction in its vicinity, which results in a local phase separation of solute particles, and the density fluctuations of solute particles cause the enhanced diffusion of the colloid. In this paper, we investigate an assembly of such active particles, using (i) an explicit model, where the microscopic dynamics of the solute particles is accounted for; and (ii) an implicit model, whose parameters are inferred from the explicit model at infinite dilution. In the explicit solute model, the effective diffusion coefficient of the active colloids strongly decreases with density, an effect which is not captured by the derived implicit model. This suggests that classical models, which usually decouple pair interactions from activity, fail to describe collective dynamics in active colloidal systems driven by solute-solute interactions.

cond-mat.soft↗

arXiv2023

Exact spatial correlations in single-file diffusion

Single-file diffusion refers to the motion of diffusive particles in narrow channels, so that they cannot bypass each other. This constraint leads to the subdiffusion of a tagged particle, called the tracer. This anomalous behaviour results from the strong correlations that arise in this geometry between the tracer and the surrounding bath particles. Despite their importance, these bath-tracer correlations have long remained elusive, because their determination is a complex many-body problem. Recently, we have shown that, for several paradigmatic models of single-file diffusion such as the Simple Exclusion Process, these bath-tracer correlations obey a simple exact closed equation. In this paper, we provide the full derivation of this equation, as well as an extension to another model of single-file transport: the double exclusion process. We also make the connection between our results and the ones obtained very recently by several other groups, and which rely on the exact solution of different models obtained by the inverse scattering method.

cond-mat.stat-mech↗

arXiv2023

Driven Tracer in the Symmetric Exclusion Process: Linear Response and Beyond

Tracer dynamics in the Symmetric Exclusion Process, where hardcore particles diffuse on an infinite one-dimensional lattice, is a paradigmatic model of anomalous diffusion. While the equilibrium situation has received a lot of attention, the case where the tracer is driven by an external force, which provides a minimal model of nonequilibrium transport in confined crowded environments, remains largely unexplored. Indeed, the only available analytical results concern the means of both the position of the tracer and the lattice occupation numbers in its frame of reference, and higher-order moments but only in the high-density limit. Here, we provide a general hydrodynamic framework that allows us to determine the first cumulants of the bath-tracer correlations and of the tracer's position in function of the driving force, up to quadratic order (beyond linear response). This result constitutes the first determination of the bias-dependence of the variance of a driven tracer in the SEP for an arbitrary density. The framework presented here can be applied, beyond the SEP, to more general configurations of a driven tracer in interaction with obstacles in one dimension.

cond-mat.stat-mech↗

arXiv2023

Duality relations in single-file diffusion

Single-file transport, which corresponds to the diffusion of particles that cannot overtake each other in narrow channels, is an important topic in out-of-equilibrium statistical physics. Various microscopic models of single-file systems have been considered, such as the simple exclusion process, which has reached the status of a paradigmatic model. Several different models of single-file diffusion have been shown to be related by a duality relation, which holds either microscopically or only in the hydrodynamic limit of large time and large distances. Here, we show that, within the framework of fluctuating hydrodynamics, these relations are not specific to these models and that, in the hydrodynamic limit, every single-file system can be mapped onto a dual single-file system, which we characterise. This general duality relation allows us to obtain new results for different models, by exploiting the solutions that are available for their dual model.

cond-mat.stat-mech↗

arXiv2022

Diffusion of a tracer in a dense mixture of soft particles connected to different thermostats

We study the dynamics of a tracer in a dense mixture of particles connected to different thermostats. Starting from the overdamped Langevin equations that describe the evolution of the system, we derive the expression of the self-diffusion coefficient of a tagged particle in the suspension, in the limit of soft interactions between the particles. Our derivation, which relies on the linearization of the Dean-Kawasaki equations obeyed by the density fields and on a path-integral representation of the dynamics of the tracer, extends previous derivations that held for tracers in contact with a single bath. Our analytical result is confronted to results from Brownian dynamics simulations. The agreement with numerical simulations is very good even for high densities. We show how the diffusivity of tracers can be affected by the activity of a dense environment of soft particles that may represent polymer coils -- a result that could be of relevance in the interpretation of measurements of diffusivity in biological media. Finally, our analytical result is general and can be applied to the diffusion of tracers coupled to different types of fluctuating environments, provided that their evolution equations are linear and that the coupling between the tracer and the bath is weak.

cond-mat.soft↗

arXiv2022

Conditions for the propulsion of a colloid surrounded by a mesoscale phase separation

We study a two-dimensional model of an active isotropic colloid whose propulsion is linked to the interactions between solute particles of the bath. The colloid catalyzes a chemical reaction in its vicinity, that yields a local phase separation of solute particles. The density fluctuations of solute particles result in the enhanced diffusion of the colloid. Using numerical simulations, we thoroughly investigate the conditions under which activity occurs, and we establish a state diagram for the activity of the colloid as a function of the parameters of the model. We use the generated data to unravel a key observable that controls the existence and the intensity of activity: the filling fraction of the reaction area. Remarkably, we finally show that propulsion also occurs in three-dimensional geometries, which confirms the interest of this mechanism for experimental applications.

cond-mat.soft↗

arXiv2022

Absolute negative mobility of an active tracer in a crowded environment

Absolute negative mobility (ANM) refers to the situation where the average velocity of a driven tracer is opposite to the direction of the driving force. This effect was evidenced in different models of nonequilibrium transport in complex environments, whose description remains effective. Here, we provide a microscopic theory for this phenomenon. We show that it emerges in the model of an active tracer particle submitted to an external force, and evolving on a discrete lattice populated with mobile passive crowders. Resorting to a decoupling approximation, we compute analytically the velocity of the tracer particle as a function of the different parameters of the system, and confront our results to numerical simulations. We determine the range of parameters where ANM can be observed, characterize the response of the environment to the displacement of the tracer, and clarify the mechanism underlying ANM and its relationship with negative differential mobility (another hallmark of driven systems far from the linear response).

cond-mat.soft↗

arXiv2022

Exact time dependence of the cumulants of a tracer position in a dense lattice gas

We develop a general method to calculate the exact time dependence of the cumulants of the position of a tracer particle in a dense lattice gas of hardcore particles. More precisely, we calculate the cumulant generating function associated with the position of a tagged particle at arbitrary time, and at leading order in the density of vacancies on the lattice. In particular, our approach gives access to the short-time dynamics of the cumulants of the tracer position -- a regime in which few results are known. The generality of our approach is demonstrated by showing that it goes beyond the case of a symmetric 1D random walk, and covers the important situations of (i) a biased tracer; (ii) comb-like structures; and (iii) $d$-dimensional situations.

cond-mat.stat-mech↗

arXiv2022

Exact closure and solution for spatial correlations in single-file diffusion

Single-file transport, where particles diffuse in narrow channels while not overtaking each other, is a fundamental model for the tracer subdiffusion observed in confined systems, such as zeolites or carbon nanotubes. This anomalous behavior originates from strong bath-tracer correlations in 1D, which, despite extensive effort, have however remained elusive, because they involve an infinite hierarchy of equations. Here, for the Symmetric Exclusion Process, a paradigmatic model of single-file diffusion, we break the hierarchy and unveil a closed exact equation satisfied by these correlations, which we solve. Beyond quantifying the correlations, the central role of this key equation as a novel tool for interacting particle systems is further demonstrated by showing that it applies to out-of equilibrium situations, other observables and other representative single-file systems.

cond-mat.stat-mech↗

arXiv2021

Microscopic theory for the diffusion of an active particle in a crowded environment

We calculate the diffusion coefficient of an active tracer in a schematic crowded environment, represented as a lattice gas of passive particles with hardcore interactions. Starting from the master equation of the problem, we put forward a closure approximation that goes beyond trivial mean-field and provides the diffusion coefficient for an arbitrary density of crowders in the system. We show that our approximation is accurate for a very wide range of parameters, and that it correctly captures numerous nonequilibrium effects, which are the signature of the activity in the system. In addition to the determination of the diffusion coefficient of the tracer, our approach allows us to characterize the perturbation of the environment induced by the displacement of the active tracer. Finally, we consider the asymptotic regimes of low and high densities, in which the expression of the diffusion coefficient of the tracer becomes explicit, and which we argue to be exact.

cond-mat.stat-mech↗

arXiv2021

Synchronization and enhanced catalysis of mechanically coupled enzymes

We examine the stochastic dynamics of two enzymes that are mechanically coupled to each other, e.g., through an elastic substrate or a fluid medium. The enzymes undergo conformational changes during their catalytic cycle, which itself is driven by stochastic steps along a biased chemical free energy landscape. We find conditions under which the enzymes can synchronize their catalytic steps, and discover that the coupling can lead to a significant enhancement in their overall catalytic rate. Both effects can be understood as arising from a global bifurcation in the underlying dynamical system at sufficiently strong coupling. Our findings suggest that, despite their molecular scale, enzymes can be cooperative and improve their performance in metabolic clusters.

cond-mat.stat-mech↗

arXiv2021

Comment on "Relative Diffusivities of Bound and Unbound Protein Can Control Chemotactic Directionality''

This is a comment on a recently published paper in Langmuir: Mandal, N. S.; Sen, A. Relative Diffusivities of Bound and Unbound Protein Can Control Chemotactic Directionality. Langmuir 2021, PMID: 34647749 [arXiv:2103.13469]. In this study, Mandal and Sen claim to propose a new kinetic model to analyze the directional movement of enzyme molecules in response to a gradient of their substrate, with the supposedly new prediction that net movement occurs up the substrate gradient when the diffusivity of the substrate-bound enzyme is lower than that of the unbound enzyme, and movement down the substrate gradient when the diffusivity of the substrate-bound enzyme is higher than that of the unbound enzyme. They develop this theoretical scheme to present an alternative to our previously published theoretical framework [Agudo-Canalejo, J.; Illien, P.; Golestanian, R. Phoresis and enhanced diffusion compete in enzyme chemotaxis. Nano Lett. 2018, 18, 2711-2717; arXiv:2104.02394]. We demonstrate that despite their claim, what they present is exactly the same theory as our work, and therefore, we conclude that their claim of novelty is unsubstantiated.

physics.bio-ph↗

arXiv2021

Generalised density profiles in single-file systems

Single-file diffusion refers to the motion in narrow channels of particles which cannot bypass each other. These strong correlations between particles lead to tracer subdiffusion, which has been observed in contexts as varied as transport in porous media, zeolites or confined colloidal suspensions, and theoretically studied in numerous works. Most approaches to this celebrated many-body problem were restricted to the description of the tracer only, whose essential properties, such as large deviation functions or two-time correlation functions, were determined only recently. Here, we go beyond this standard description by introducing and determining analytically generalised density profiles (GDPs) in the frame of the tracer. In addition to controlling the statistical properties of the tracer, these quantities fully characterise the correlations between the tracer position and the bath particles density. Considering the hydrodynamic limit of the problem, we unveil universal scaling properties of the GDPs with space and time, and a non-monotonic dependence with the distance to the tracer despite the absence of any asymmetry. Our analytical approach provides exact results for the GDPs of paradigmatic models of single-file diffusion, such as Brownian particles with hardcore repulsion, the Symmetric Exclusion Process and the Random Average Process. The range of applicability of our approach is further illustrated by considering extensions to general interactions between particles and out-of-equilibrium situations.

cond-mat.stat-mech↗

arXiv2021

Spontaneous propulsion of an isotropic colloid in a phase-separating environment

The motion of active colloids is generally achieved through their anisotropy, as exemplified by Janus colloids. Recently, there was a growing interest in the propulsion of isotropic colloids, which requires some local symmetry breaking. Although several mechanisms for such propulsion were proposed, little is known about the role played by the interactions within the environment of the colloid, which can have a dramatic effect on its propulsion. Here, we propose a minimal model of an isotropic colloid in a bath of solute particles that interact with each other. These interactions lead to a spontaneous phase transition close to the colloid, to directed motion of the colloid over very long timescales and to significantly enhanced diffusion, in spite of the crowding induced by solute particles. We determine the range of parameters where this effect is observable in the model, and we propose an effective Langevin equation that accounts for it and allows one to determine the different contributions at stake in self-propulsion and enhanced diffusion.

cond-mat.soft↗

arXiv2021

'Fuelled' motion: phoretic motility and collective behaviour of active colloids

Designing microscopic and nanoscopic self-propelled particles and characterising their motion has become a major scientific challenge over the past decades. To this purpose, phoretic effects, namely propulsion mechanisms relying on local field gradients, have been the focus of many theoretical and experimental studies. In this review, we adopt a tutorial approach to present the basic physical mechanisms at stake in phoretic motion, and describe the different experimental works that lead to the fabrication of active particles based on this principle. We also present the collective effects observed in assemblies of interacting active colloids, and the theoretical tools that have been used to describe phoretic and hydrodynamic interactions.

cond-mat.soft↗

arXiv2021

Enhanced diffusion and chemotaxis at the nanoscale

Enzymes have been recently proposed to have mechanical activity associated with their chemical activity. In a number of recent studies, it has been reported that enzymes undergo enhanced diffusion in the presence of their corresponding substrate, when this substrate is uniformly distributed in solution. Moreover, if the concentration of the substrate is non-uniform, enzymes and other small molecules have been reported to show chemotaxis -- biased stochastic movement in the direction of the substrate gradient -- typically towards higher concentrations of this substrate, with a few exceptions. The underlying physical mechanisms responsible for enhanced diffusion and chemotaxis at the nanoscale, however, are still not well understood. Understanding these processes is important both for fundamental biological research, e.g. in the context of spatial organization of enzymes in metabolic pathways (metabolon formation), as well as for engineering applications, such as in the design of new vehicles for targeted drug delivery. In this Account, we will review the available experimental observations of both enhanced diffusion and chemotaxis, and we will discuss critically the different theories that have been proposed to explain the two. We first focus on enhanced diffusion, beginning with an overview of the experimental results. We then discuss the two main types of mechanisms that have been proposed, namely active mechanisms relying on the catalytic step of the enzymatic reaction, and equilibrium mechanisms which consider the reversible binding and unbinding of the substrate to the enzyme. We put particular emphasis on an equilibrium model recently introduced by us, which describes how the diffusion of dumbbell-like modular enzymes can be enhanced in the presence of substrate, thanks to a binding-induced reduction of the internal fluctuations of the enzyme. We then turn to chemotaxis, [...]

physics.bio-ph↗

arXiv2021

Phoresis and Enhanced Diffusion Compete in Enzyme Chemotaxis

Chemotaxis of enzymes in response to gradients in the concentration of their substrate has been widely reported in recent experiments, but a basic understanding of the process is still lacking. Here, we develop a microscopic theory for chemotaxis, valid for enzymes and other small molecules. Our theory includes both non-specific interactions between enzyme and substrate, as well as complex formation through specific binding between the enzyme and the substrate. We find that two distinct mechanisms contribute to enzyme chemotaxis: a diffusiophoretic mechanism due to the non-specific interactions, and a new type of mechanism due to binding-induced changes in the diffusion coefficient of the enzyme. The latter chemotactic mechanism points towards lower substrate concentration if the substrate enhances enzyme diffusion, and towards higher substrate concentration if the substrate inhibits enzyme diffusion. For a typical enzyme, attractive phoresis and binding-induced enhanced diffusion will compete against each other. We find that phoresis dominates above a critical substrate concentration, whereas binding-induced enhanced diffusion dominates for low substrate concentration. Our results resolve an apparent contradiction regarding the direction of urease chemotaxis observed in experiments, and in general clarify the relation between enhanced diffusion and chemotaxis of enzymes. Finally, we show that the competition between the two distinct chemotactic mechanisms may be used to engineer nanomachines that move towards or away from regions with a specific substrate concentration.

physics.bio-ph↗