Publications

Two hallmarks of nonequilibrium systems, from active colloids to animal herds, are agent motility and nonreciprocal interactions. Their interplay creates feedback loops that lead to complex spatiotemporal dynamics crucial to understand and control the nonlinear response of active systems. Here, we introduce a minimal model that captures these two features at the microscopic scale while admitting an exact hydrodynamic theory valid also in the fully nonlinear regime. Using statistical mechanics techniques, we exactly coarse-grain our nonreciprocal microscopic model into a fluctuating hydrodynamics and use dynamical systems insights to analyze the resulting equations. In the absence of motility, we find two transitions to oscillatory phases occurring via distinct mechanisms: a Hopf bifurcation and a saddle node on invariant circle bifurcation. In the presence of motility, this rigorous approach, complemented by numerical simulations, allows us to quantitatively assess the hitherto neglected impact of interspecies nonreciprocity on a paradigmatic transition in active matter: the emergence of collective motion. When nonreciprocity is weak, we show that flocking is accelerated and bands tend to synchronize with a spatial overlap controlled by nonlinearities. When nonreciprocity is strong, flocking is superseded by a chase and rest dynamical phase, where each species alternates between a chasing state, when they propagate, and a resting state, when they stand still. Phenomenological models with linear nonreciprocal couplings fail to predict the chase and rest phase, which illustrates the usefulness of our exact coarse-graining procedure. Finally, we demonstrate how fluctuations in finite systems can be harnessed to characterize microscopic nonreciprocity from macroscopic time-correlation functions, even in phases where nonreciprocal interactions do not affect the thermodynamic steady state.

Nonreciprocal interactions are widely observed in nonequilibrium systems, from biological or sociological dynamics to open quantum systems. Despite the ubiquity of nonreciprocity, its impact on phase transitions is not fully understood. In this work, we derive criteria to perturbatively assess whether nonreciprocity changes the universality class of pairs of asymmetrically coupled systems undergoing a phase transition. These simple criteria are stated in terms of the unperturbed critical exponents, in the spirit of the Harris criterion for disordered systems, and agree with numerical simulations. Beyond nonreciprocity, our approach provides guidelines for assessing how dynamical phase transitions are affected by perturbations.

Living systems display complex behaviors driven by physical forces as well as decision-making. Hydrodynamic theories hold promise for simplified universal descriptions of socially generated collective behaviors. However, the construction of such theories is often divorced from the data they should describe. Here, we develop and apply a data-driven pipeline that links micromotives to macrobehavior by augmenting hydrodynamics with individual preferences that guide motion. We illustrate this pipeline on a case study of residential dynamics in the United States, for which census and sociological data are available. Guided by Census data, sociological surveys, and neural network analysis, we systematically assess standard hydrodynamic assumptions to construct a sociohydrodynamic model. Solving our minimal hydrodynamic model, calibrated using statistical inference, qualitatively captures key features of residential dynamics at the level of individual US counties. We highlight that a social memory, akin to hysteresis in magnets, emerges in the segregationintegration transition even with memory-less agents. While residential segregation is a multifactorial phenomenon, this physics analogy suggests a simple mechanistic explanation for the phenomenon of neighborhood tipping, whereby a small change in a neighborhoods population leads to a rapid demographic shift. Beyond residential segregation, our work paves the way for systematic investigations of decision-guided motility in real space, from micro-organisms to humans, as well as fitness-mediated motion in more abstract spaces.

Systems with nonreciprocal interactions generically display time-dependent states. These are routinely observed in finite systems, from neuroscience to active matter, in which globally ordered oscillations exist. However, the stability of these uniform nonreciprocal phases in noisy spatially-extended systems, their fate in the thermodynamic limit, and the critical behavior of the corresponding phase transitions are not fully understood. Here, we address these questions by introducing a nonreciprocal generalization of the Ising model and study its phase transitions by means of numerical and analytical approaches. While the mean-field equations predict three stable homogeneous phases (disordered, ordered, and a time-dependent swap phase), our large scale numerical simulations reveal a more complex picture. Static order is destroyed in any finite dimension due to the growth of rare droplets unless the symmetry between the two spin types is broken, triggering a stabilizing droplet-capture mechanism. The swap phase is destroyed by fluctuations in two dimensions through the proliferation of spiral defects but stabilized in three dimensions, where nonreciprocity changes the critical exponents from Ising to XY, thus giving rise to a robust spatially-distributed clock.

Nonreciprocal interactions in many-body systems lead to time-dependent states, commonly observed in biological, chemical, and ecological systems. The stability of these states in the thermodynamic limit and the critical behavior of the phase transition from static to time-dependent states are not yet fully understood. To address these questions, we study a minimalistic system endowed with nonreciprocal interactions: an Ising model with two spin species having opposing goals. The mean-field equation predicts three stable phases: disorder, static order, and a time-dependent swap phase. Large-scale numerical simulations support the following: (i) in two dimensions, the swap phase is destabilized by defects; (ii) in three dimensions, the swap phase is stable and has the properties of a time crystal; (iii) the transition from disorder to swap in three dimensions is characterized by the critical exponents of the 3D XY model and corresponds to the breaking of a continuous symmetry, time translation invariance; (iv) when the two species have fully antisymmetric couplings, the static-order phase is unstable in any finite dimension due to droplet growth; and (v) in the general case of asymmetric couplings, static order can be restored by a droplet-capture mechanism preventing the droplets from growing indefinitely. We provide details on the full phase diagram, which includes first- and second-order-like phase transitions, and study how the system coarsens into swap and static-order states.

The response of ionic solutions to time-varying electric fields, quantified by a frequency-dependent conductivity, is essential in many electrochemical applications. Yet, it constitutes a challenging problem due to the combined effect of Coulombic interactions, hydrodynamics, and thermal fluctuations. Here, we study the frequency-dependent conductivity of ionic solutions using a stochastic density functional theory. In the limit of small concentrations, we recover the classical Debye and Falkenhagen (DF) result, predicting an increase in conductivity with field frequency. At higher concentrations, we use a modified Coulomb interaction potential that accounts for the hard-core repulsion between the ions, which was recently employed in the zero-frequency case. Consequently, we extend the DF result to concentrated electrolytes. We discuss experimental and numerical studies and the complexity of observing the DF effect in such setups.

We study the effects of charge-regulated acid/base equilibrium on the swelling of polyelectrolyte gels by considering a combination of the Poisson-Boltzmann theory and a two-site charge-regulation model based on the Langmuir adsorption isotherm. By exploring the volume change as a function of salt concentration for both nanogels and microgels, we identify conditions where the gel volume exhibits a discontinuous swelling transition. This transition is driven exclusively by the charge-regulation mechanism and is characterized by a closed-loop phase diagram. Our predictions can be tested experimentally for polypeptide gels.

The electric conductivity of ionic solutions is well understood at low ionic concentrations of up to a few millimolar but becomes difficult to unravel at higher concentrations that are still common in nature and technological applications. A model for the conductivity at high concentrations was recently put forth for monovalent electrolytes at low electric fields. The model relies on applying a stochastic density-functional theory and using a modified electrostatic pair-potential that suppresses unphysical, short-range electrostatic interactions. Here, we extend the theory to multivalent ions as well as to high electric fields where a deviation from Ohm's law known as the Wien effect occurs. Our results are in good agreement with experiments and recent simulations.

The conductivity of ionic solutions is arguably their most important trait, being widely used in electrochemical, biochemical, and environmental applications. The Debye-Hückel-Onsager theory successfully predicts the conductivity at very low ionic concentrations of up to a few millimolars, but there is no well-established theory applicable at higher concentrations. We study the conductivity of ionic solutions using a stochastic density functional theory, paired with a modified Coulomb interaction that accounts for the hard-core repulsion between the ions. The modified potential suppresses unphysical, short-range electrostatic interactions, which are present in the Debye-Hückel-Onsager theory. Our results for the conductivity show very good agreement with experimental data up to 3 molars, without any fit parameters. We provide a compact expression for the conductivity, accompanied by a simple analytical approximation.

Complex coacervation, known as the liquid-liquid phase separation of solutions with oppositely charged polyelectrolytes, has attracted substantial interest in recent years. We study the effect of the charge regulation (CR) mechanism on the complex coacervation by including short-range interactions between the charged sites on the polymer chains as well as an association-dissociation energy parameter in the CR mechanism. We investigate the phase diagrams of two CR models: (i) the hopping CR model (HCR) and (ii) the asymmetric CR model (ACR). It is shown that during the phase separation that the polymers in the condensed phase are more charged than those in the dilute phase, in accordance with Le Chatelier's principle. In addition, secondary CR effects also influence the change in the volume fraction of the two phases. The latter can cause the charge difference between the two phases to change nonmonotonically as a function of the CR parameters.

We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as a function of a dimensionless parameter. This parameter depends on the electrostatic properties and can be controlled by tuning the solution ionic strength. At low ionic strength, the colloid moves faster and is localized, while at high ionic strength it moves slower and explores a wider region between the walls, resulting in a larger diffusion characteristic time.

Based on a collective description of electrolytes composed of charge-regulated macro-ions and simple salt ions, we analyze their equilibrium charge state in the bulk and their behavior in the vicinity of an external electrified surface. The mean-field formulation of mobile macro-ions in an electrolyte bathing solution is extended to include interactions between association and dissociation sites. We demonstrate that above a critical concentration of salt, similar to the critical micelle concentration, a non-trivial distribution of charge states sets in. Such a charge state can eventually lead to a liquid-liquid phase separation based on charge regulation.

In spite of their enormous applications as alternative energy storage devices and lubricants, room-temperature ionic liquids (ILs) still pose many challenges from a pure scientific viewpoint. We develop an IL microscopic theory in terms of ionic clusters, which describes the IL behavior close to charged interfaces. The full structure factor of finite-size clusters is considered and allows us to retain fine and essential details of the system as a whole. Beside the reduction in the screening, it is shown that ionic clusters cause the charge density to oscillate near charged boundaries, with alternating ion-size thick layers, in agreement with experiments. We distinguish between short-range oscillations that persist for a few ionic layers close to the boundary, as opposed to long-range damped oscillations that hold throughout the bulk. The former can be captured by finite-size ion pairs, while the latter is associated with larger clusters with a pronounced quadrupole (or higher) moment. The long-wavelength limit of our theory recovers the well-known Bazant-Storey-Kornyshev (BSK) equation in the linear regime, and elucidates the microscopic origin of the BSK phenomenological parameters.

Planet formation begins with collisional growth of small planetesimals accumulating into larger ones. Such growth occurs while planetesimals are embedded in a gaseous protoplanetary disc. However, small planetesimals experience collisions and gas drag that lead to their destruction on short time-scales, not allowing, or requiring fine-tuned conditions for the efficient growth of ∼metre-sized objects. Here we show that ∼10⁴ interstellar objects such as the recently detected 1I/2017-U1 ('Oumuamua) could have been captured, and become part of the young Solar system, together with up to hundreds of ∼km-sized ones. The capture rates are robust even for conservative assumptions on the protoplanetary disc structure, local stellar environment, and planetesimal interstellar medium density. 'Seeding' of such planetesimals then catalyses further planetary growth into planetary embryos, and potentially alleviates the main challenges with the metre-sized growth barrier. The capture model is in synergy with the current leading planet formation theories, providing the missing link to the first planetesimals. Moreover, planetesimal capture provides a far more efficient route for lithopanspermia than previously thought.

Uncompensated charges do not usually occur in Nature and any local charge should be a result of charge separation. Dissociable chemical groups at interfaces in contact with ions in solution, whose chemical equilibrium depends both on short-range non-electrostatic and long-range electrostatic interactions, are the physical basis of this charge separation, known as charge regulation phenomena. The charged groups can be either fixed and immobile, as in the case of solvent-exposed solid substrate and soft bounding surfaces (e.g., atomically smooth mica surfaces and soft phospholipid membranes), or free and mobile, as in the case of charged macro-ions (e.g., protein or other biomolecules). Here, we review the mean-field formalism used to describe both cases, with a focus on recent advances in the modeling of mobile charge-regulated macro-ions in an ionic solution. The general form of the screening length is derived, and is shown to combine the concept of intrinsic capacitance (introduced by Lund and Jönsson) with bulk capacitance, resulting from the mobility of small ions and macro-ions. The advantages and disadvantages of different formulations, such as the cell model vs. the collective approach, are discussed, along with several suggestions for future experiments and modeling.

The most well-known manifestation of the Casimir effect is the attraction of two uncharged conducting plates. However, it turns out that Casimir forces are all around us: they originate from vacuum fluctuations of the electromagnetic field that excite dipoles in dielectric and conducting materials. These dipoles then interact with each other, generating measurable forces between macroscopic bodies: the Casimir force. A naive calculation of the Casimir force produces infinities, and though extensive work has been done in the field, there is still no universal prescription to renormalize the force. In this paper, we introduce the subject of Casimir forces and focus on the Casimir self-stress inside a homogeneous sphere. We discuss previous calculations and suggest an additional renormalization scheme that could solve the problem.

We revisit the charge-regulation mechanism of macro-ions and apply it to mobile macro-ions in a bathing salt solution. In particular, we examine the effects of correlation between various adsorption/desorption sites and analyze the collective behavior in terms of the solution effective screening properties. We show that such a behavior can be quantified in terms of the charge asymmetry of the macro-ions, defined by their preference for a non-zero effective charge, and their donor/acceptor propensity for exchanging salt ions with the bathing solution. Asymmetric macro-ions tend to increase the screening, while symmetric macro-ions can in some cases decrease it. Macro-ions that are classified as donors display a rather regular behavior, while those that behave as acceptors exhibit an anomalous non-monotonic Debye length. The screening properties, in their turn, engender important modifications to the disjoining pressure between two charged surfaces. Our findings are in particular relevant for solutions of proteins, whose exposed amino acids can undergo charge dissociation/association processes to/from the bathing solution, and can be considered as a solution of charged regulated macro-ions, as analyzed here.

The dielectric sphere has been an important test case for understanding and calculating the vacuum force of a dielectric body onto itself. Here we develop a method for computing this force in homogeneous spheres of arbitrary dielectric properties embedded in arbitrary homogeneous backgrounds, assuming only that both materials are isotropic and dispersionless. Our results agree with known special cases; most notably we reproduce the prediction of Boyer and Schwinger et al. of a repulsive Casimir force of a perfectly reflecting shell. Our results disagree with the literature in the dilute limit. We argue that the Casimir self-stress cannot be regarded as due to pair-wise CasimirPolder interactions, but rather due to reflections of virtual electromagnetic waves.