arXiv subjects

Nicoletta Gnan

Publications and source records attributed to Nicoletta Gnan.

At least 37 records · Page 2Linked to original sources

arXiv2019

"In silico" synthesis of microgel particles

Microgels are colloidal-scale particles individually made of crosslinked polymer networks that can swell and deswell in response to external stimuli, such as changes to temperature or pH. Despite a large amount of experimental activities on microgels, a proper theoretical description based on individual particle properties is still missing due to the complexity of the particles. To go one step further, here we propose a novel methodology to assemble realistic microgel particles "in silico". We exploit the self-assembly of a binary mixture composed of tetravalent (crosslinkers) and bivalent (monomer beads) patchy particles under spherical confinement in order to produce fully-bonded networks. The resulting structure is then used to generate the initial microgel configuration, which is subsequently simulated with a bead-spring model complemented by a temperature-induced hydrophobic attraction. To validate our assembly protocol we focus on a small microgel test-case and show that we can reproduce the experimental swelling curve by appropriately tuning the confining sphere radius, something that would not be possible with less sophisticated assembly methodologies, e.g. in the case of networks generated from an underlying crystal structure. We further investigate the structure (in reciprocal and real space) and the swelling curves of microgels as a function of temperature, finding that our results are well described by the widely-used fuzzy sphere model. This is a first step toward a realistic modelling of microgel particles, which will pave the way for a careful assessment of their elastic properties and effective interactions.

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arXiv2019

Modelling realistic microgels in an explicit solvent

Thermoresponsive microgels are polymeric colloidal networks that can change their size in response to a temperature variation. This peculiar feature is driven by the nature of the solvent-polymer interactions, which triggers the so-called volume phase transition from a swollen to a collapsed state above a characteristic temperature. Recently, an advanced modelling protocol to assemble realistic, disordered microgels has been shown to reproduce experimental swelling behavior and form factors. In the original framework, the solvent was taken into account in an implicit way, condensing solvent-polymer interactions in an effective attraction between monomers. To go one step further, in this work we perform simulations of realistic microgels in an explicit solvent. We identify a suitable model which fully captures the main features of the implicit model and further provides information on the solvent uptake by the interior of the microgel network and on its role in the collapse kinetics. These results pave the way for addressing problems where solvent effects are dominant, such as the case of microgels at liquid-liquid interfaces.

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arXiv2019

Effective potentials induced by self-assembly of patchy particles

Effective colloid-colloid interactions can be tailored through the addition of a complex cosolute. Here we investigate the case of a cosolute made by self-assembling patchy particles. Depending on the valence, these particles can form either polymer chains or branched structures. We numerically calculate the effective potential $V_{eff}$ between two colloids immersed in a suspension of reversible patchy particles, exploring a wide region of the cosolute phase diagram and the role of valence. In addition to well-known excluded volume and depletion effects, we find that, under appropriate conditions, $V_{eff}$ is completely attractive but shows an oscillatory character. In the case of polymerizing cosolute, this results from the fact that chains are efficiently confined by the colloids through the onset of local order. This argument is then generalized to the case of particles with higher valence, under the condition that they are still able to maintain a fully bonded organization upon confinement. The resulting effective potentials are relevant for understanding the behavior of complex mixtures in crowded environments, but may also be exploited for tuning colloidal self-assembly at preferred target distances in order to build desired superstructures.

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arXiv2019

Rheological investigation of gels formed by competing interactions: A numerical study

A transition from solid-like to liquid-like behavior occurs when colloidal gels are subjected to a prolonged exposure to a steady shear. This phenomenon, which is characterized by a yielding point, is found to be strongly dependent on the packing fraction. However, it is not yet known how the effective inter-particle potential affects this transition. To this aim, we present a numerical investigation of the rheology of equilibrium gels in which a short-range depletion is complemented by a long-range electrostatic interaction. We observe a single yielding event in the stress-strain curve, occurring at a fixed strain. The stress overshoot is found to follow a power-law dependence on the Péclet number, with an exponent larger than that found in depletion gels, suggesting that its value may depend systematically on the underlying colloid-colloid interactions. We also establish a mapping between equilibrium states and steady states under shear, which allows us to identify the structural modifications induced by the presence of the shear. Remarkably, we find that steady states corresponding to the same Péclet number, obtained by different combinations of shear rate and solvent viscosity, show identical structural and rheological properties. Our results highlight the importance of understanding the coupling between colloidal interactions, solvent effects, and flow to be able to describe the microscopic organization of colloidal particles under shear.

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arXiv2017

Discontinuous change from thermally- to geometrically- dominated effective interactions in colloidal solutions

We report numerical results for the effective potential arising between two colloids immersed in a self-assembling cosolute which forms reversible clusters. The potential is evaluated at cosolute state points with different densities and temperatures but with the same connectivity properties. We find that the range of the resulting effective potential is controlled only by the cosolute thermal correlation length rather than by its connectivity length. We discuss the significant differences with previous results focused on cosolute forming irreversible clusters and we show that irreversible bond case represents a singular limit which cannot be accessed in equilibrium by continuously increasing the bond lifetime.

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arXiv2017

Dynamical and structural signatures of the glass transition in emulsions

We investigate structural and dynamical properties of moderately polydisperse emulsions across an extended range of droplet volume fractions phgr, encompassing fluid and glassy states up to jamming. Combining experiments and simulations, we show that when $ϕ$ approaches the glass transition volume fraction ${ϕ_{g}}$ , dynamical heterogeneities and amorphous order arise within the emulsion. In particular, we find an increasing number of clusters of particles having five-fold symmetry (i.e. the so-called locally favoured structures, LFS) as $ϕ$ approaches ${ϕ_{g}}$ , saturating to a roughly constant value in the glassy regime. However, contrary to previous studies, we do not observe a corresponding growth of medium-range crystalline order; instead, the emergence of LFS is decoupled from the appearance of more ordered regions in our system. We also find that the static correlation lengths associated with the LFS and with the fastest particles can be successfully related to the relaxation time of the system. By contrast, this does not hold for the length associated with the orientational order. Our study reveals the existence of a link between dynamics and structure close to the glass transition even in the absence of crystalline precursors or crystallization. Furthermore, the quantitative agreement between our confocal microscopy experiments and Brownian dynamics simulations indicates that emulsions are and will continue to be important model systems for the investigation of the glass transition and beyond.

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arXiv2016

Critical Phenomena in Active Matter

We investigate the effect of self-propulsion on a mean-field order-disorder transition. Starting from a $φ^4$ scalar field theory subject to an exponentially correlated noise, we exploit the Unified Colored Noise Approximation to map the non-equilibrium active dynamics onto an effective equilibrium one. This allows us to follow the evolution of the second-order critical point as a function of the noise parameters: the correlation time $τ$ and the noise strength $D$. Our results suggest that $τ$ is a crucial ingredient that changes the location of the critical point but, remarkably, not the universality class of the model. We also estimate the effect of Gaussian fluctuations on the mean-field approximation finding an Ornstein-Zernike like expression for the static structure factor at long wave lengths. Finally, to assess the validity of our predictions, we compare the mean-field theoretical results with numerical simulations of active Lennard-Jones particles in two and three dimensions, finding a good qualitative agreement at small $τ$ values.

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arXiv2015

Velocity distribution in active particles systems

We derive an analytic expression for the distribution of velocities of multiple interacting active particles which we test by numerical simulations. In clear contrast with equilibrium we find that the velocities are coupled to positions. Our model shows that, even for two particles only, the individual velocities display a variance depending on the interparticle separation and the emergence of correlations between the velocities of the particles. When considering systems composed of many particles we find an analytic expression connecting the overall velocity variance to density, at the mean-field level, and to the pair distribution function valid in the limit of small noise correlation times. Finally we discuss the intriguing analogies and main differences between our effective free energy functional and the theoretical scenario proposed so far for phase-separating active particles.

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arXiv2015

Multidimensional Stationary Probability Distribution for Interacting Active Particles

We derive the stationary probability distribution for a non-equilibrium system composed by an arbitrary number of degrees of freedom that are subject to Gaussian colored noise and a conservative potential. This is based on a multidimensional version of the Unified Colored Noise Approximation. By comparing theory with numerical simulations we demonstrate that the theoretical probability density quantitatively describes the accumulation of active particles around repulsive obstacles. In particular, for two particles with repulsive interactions, the probability of close contact decreases when one of the two particle is pinned. Moreover, in the case of isotropic confining potentials, the radial density profile shows a non trivial scaling with radius. Finally we show that the theory well approximates the "pressure" generated by the active particles allowing to derive an equation of state for a system of non-interacting colored noise-driven particles.

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arXiv2014

How soft repulsion enhances the depletion mechanism

We investigate binary mixtures of large colloids interacting through soft potentials with small, ideal depletants. We show that softness has a dramatic effect on the resulting colloid-colloid effective potential when the depletant-to-colloid size ratio $q$ is small, with significant consequences on the colloidal phase behaviour. We also provide an exact relation that allows us to obtain the effective pair potential for {\it any} type of colloid-depletant interactions in the case of ideal depletants, without having to rely on complicated and expensive full-mixture simulations. We also show that soft repulsion among depletants further enhances the tendency of colloids to aggregate. Our theoretical and numerical results demonstrate that --- in the limit of small $q$ --- soft mixtures cannot be mapped onto hard systems and hence soft depletion is not a mere extension of the widely used Asakura-Oosawa potential.

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arXiv2014

Multiple higher-order singularities and iso-dynamics in a simple glass-former model

We investigate the slow dynamics of a colloidal model with two repulsive length scales, whose interaction potential is the sum of a hard-core and a square shoulder. Despite the simplicity of the interactions, Mode-Coupling theory predicts a complex dynamic scenario: a fluid-glass line with two reentrances and a glass-glass line ending with multiple higher-order ($A_3$ or $A_4$) singularities. In this work we verify the existence of the two $A_4$ points by numerical simulations, observing subdiffusive behaviour of the mean-square displacement and logarithmic decay of the density correlators. Surprisingly, we also discover a novel dynamic behaviour generated by the competition between the two higher-order singularities. This results in the presence of special loci along which the dynamics is identical \textit{at all} length and time scales.

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arXiv2014

Casimir-like forces at the percolation transition

Percolation and critical phenomena show common features such as scaling and universality. Colloidal particles, immersed in a solvent close to criticality, experience long-range effective forces, named critical Casimir forces. %These originate from the confinement of the solvent critical fluctuations between the colloids. Building on the analogy between critical phenomena and percolation, we explore the possibility of observing long-range forces near a percolation threshold. To this aim we numerically evaluate the effective potential between two colloidal particles dispersed in a chemical sol and we show that it becomes attractive and long-ranged on approaching the sol percolation transition. We develop a theoretical description based on a polydisperse Asakura-Oosawa model which captures the divergence of the interaction range, allowing us to interpret such effect in terms of depletion interactions in a structured solvent. Our results provide the geometric analogue of the critical Casimir force, suggesting a novel way for tuning colloidal interactions by controlling the clustering properties of the solvent.

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arXiv2014

Observable-dependence of the effective temperature in off-equilibrium diatomic molecular liquids

We discuss the observable-dependence of the effective temperature $T_{eff}$, defined via the fluctuation-dissipation relation, of an out-of-equilibrium system composed by homonuclear dumbbell molecules. $T_{eff}$ is calculated by evaluating the fluctuation and the response for two observables associated respectively to translational and to rotational degrees of freedom, following a sudden temperature quench. We repeat our calculation for different dumbbell elongations $ζ$. At high elongations ($ζ> 0.4 $), we find the same $T_{eff}$ for the two observables. At low elongations ($ζ\leq 0.4$), only for very deep quenches $T_{eff}$ coincides. The observable-dependence of $T_{eff}$ for low elongations and shallow quenches stresses the importance of a strong coupling between orientational and translational variables for a consistent definition of the effective temperature in glassy systems.

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arXiv2013

Critical Casimir forces and colloidal aggregation: A numerical study

We present a numerical study of the effective potential $V_\mathrm{eff}$ between two hard-sphere colloids dispersed in a solvent of interacting particles, for several values of temperature and solvent density, approaching the solvent gas-liquid critical point. We investigate the stability of a system of particles interacting via $V_\mathrm{eff}$ to evaluate the locus of colloidal aggregation in the solvent phase-diagram, and its dependence on the colloid size. We assess how the excluded volume depletion forces are modified by solvent attraction and discuss under which conditions solvent critical fluctuations, in the form of critical Casimir forces, can be used to effectively manipulate colloidal aggregation.

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arXiv2013

Unveiling the complex glassy dynamics of square shoulder systems: simulations and theory

We performed extensive molecular dynamics (MD) simulations, supplemented by Mode Coupling Theory (MCT) calculations, for the Square Shoulder (SS) model, a purely repulsive potential where the hard-core is complemented by a finite shoulder. For the one-component version of this model, MCT predicted [Sperl {\it et al.} Phys. Rev. Lett. {\bf 104}, 145701 (2010)] the presence of diffusion anomalies both upon cooling and upon compression and the occurrence of glass-glass transitions. In the simulations, we focus on a non-crystallising binary mixture, which, at the investigated shoulder width, shows a non-monotonic behaviour of the diffusion upon cooling but not upon isothermal compression. In addition, we find the presence of a disconnected glass-glass line in the phase diagram, ending in two higher-order singularities. These points generate a logarithmic dependence of the density correlators as well as a subdiffusive behaviour of the mean squared displacement, although with the interference of the nearby liquid-glass transition. We also perform novel MCT calculations using as input the partial structure factors obtained within MD, confirming the simulation results. The presence of two hard sphere glasses, differing only in their hard core length, is revealed, showing that the simple competition between the two is sufficient for creating a rather complex dynamical behaviour.

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arXiv2012

Generalized Fluctuation-Dissipation Relation and Effective Temperature upon Heating a Deeply Supercooled Liquid

We show that a generalized fluctuation-dissipation relation applies upon instantaneously increasing the temperature of a deeply supercooled liquid. This has the same two-step shape of the relation found upon cooling the liquid, but with opposite violation, indicating an effective temperature that is lower than bath temperature. We show that the effective temperature exhibits some sensible time-dependence and that it retains its connection with the partitioned phase space visited in ageing. We underline the potential relevance of our numerical results for experimental studies of the fluctuation-dissipation relation in glassy systems.

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arXiv2012

Tuning effective interactions close to the critical point in colloidal suspensions

We report a numerical investigation of two colloids immersed in a critical solvent, with the aim of quantifying the effective colloid-colloid interaction potential. By turning on an attraction between the colloid and the solvent particles we follow the evolution from the case in which the solvent density close to the colloids changes from values smaller than the bulk to values larger than the bulk. We thus effectively implement the so-called $(+,+)$ and $(-,-)$ boundary conditions defined in field theoretical approaches focused on the description of critical Casimir forces. We find that the effective potential at large distances decays exponentially, with a characteristic decay length compatible with the bulk critical correlation length, in full agreement with theoretical predictions. We also investigate the case of $(+,-)$ boundary condition, where the effective potential becomes repulsive. Our study provides a guidance for a design of the interaction potential which can be exploited to control the stability of colloidal systems.

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arXiv2012

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

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