arXiv subjects

Francesco Turci

Publications and source records attributed to Francesco Turci.

At least 19 recordsLinked to original sources

arXiv2025

Critical surface phase behavior governs hydrophobic attraction between extended solutes

Hydrophobic interactions are central to biological self-assembly and soft matter organization, yet their microscopic origins remain debated. A key hallmark is the strengthening of attraction between hydrophobic solutes with increasing temperature, a feature often attributed to entropy changes from disrupted hydrogen bonding in water. Here we present an alternative framework based on surface phase behavior, supported by extensive molecular dynamics simulations. Using metadynamics, we quantify the solvent-mediated effective potential between nanometer-scale hydrophobic solutes in the monatomic water (mW) model, the SPCE water model, and a Lennard-Jones solvent. We develop a morphometric model which incorporates a scaling theory of critical drying, linking the range and strength of hydrophobic attraction to interfacial thermodynamics and proximity to vapor-liquid coexistence. The model reproduces the effective potential across diverse solute sizes, degrees of hydrophobicity, and thermodynamic states. Our simulations recover the inverse temperature dependence of hydrophobicity, showing it arises generically from rapid thermal expansion of the solvation shell.

cond-mat.soft↗

arXiv2024

Dominating Lengthscales of Zebrafish Collective Behaviour

Collective behaviour in living systems is observed across many scales, from bacteria to insects, to fish shoals. Zebrafish have emerged as a model system amenable to laboratory study. Here we report a three-dimensional study of the collective dynamics of fifty zebrafish. We observed the emergence of collective behaviour changing between \yy{ordered} to randomised, upon \yy{adaptation} to new environmental conditions. We quantify the spatial and temporal correlation functions of the fish and identify two length scales, the persistence length and the nearest neighbour distance, that capture the essence of the behavioural changes. The ratio of the two length scales correlates robustly with the polarisation of collective motion that we explain with a reductionist model of self--propelled particles with alignment interactions.

cond-mat.stat-mech↗

arXiv2024

What is the best simulation approach for measuring local density fluctuations near solvo/hydrophobes?

Measurements of local density fluctuations are crucial to characterizing the interfacial properties of equilibrium fluids. A specific case that has been well-explored involves the heightened compressibility of water near hydrophobic entities. Commonly, a spatial profile of local fluctuation strength is constructed from measurements of the mean and variance of solvent particle number fluctuations in a set of contiguous sub-volumes of the system adjacent to the solvo/hydrophobe. An alternative measure proposed by Evans and Stewart (J. Phys.: Condens. Matter 27, 194111 (2015)) defines a local compressibility profile in terms of the chemical potential derivative of the spatial number density profile. Using Grand Canonical Monte Carlo simulation, we compare and contrast the efficacy of these two approaches for a Lennard-Jones solvent at spherical and planar solvophobic interfaces, and SPC/E water at a hydrophobic spherical solute. Our principal findings are that: (i) the local compressibility profile $\chi({\bf r})$ of Evans and Stewart is considerably more sensitive to variations in the strength of local density fluctuations than the spatial fluctuation profile $F({\bf r})$ and can resolve much more detailed structure; (ii) while the local compressibility profile is essentially independent of the choice of spatial discretization used to construct the profile, the spatial fluctuation profile exhibits strong systematic dependence on the size of the subvolumes on which the profile is defined. We clarify the origin and nature of this finite-size effect.

cond-mat.soft↗

arXiv2023

Partial and complete wetting of droplets of active Brownian particles

We study wetting droplets formed of active Brownian particles in contact with a repulsive potential barrier, in a wedge geometry. Our numerical results demonstrate a transition between partially wet and completely wet states, as a function of the barrier height, analogous to the corresponding surface phase transition in passive fluids. We analyse partially wet configurations characterised by a nonzero contact angle $\theta$ between the droplet surface and the barrier, including the average density profile and its fluctuations. These findings are compared with two equilibrium systems: a Lennard-Jones fluid and a simple contour model for a liquid-vapour interface. We locate the wetting transition where $\cos(\theta)=1$, and the neutral state where $\cos(\theta)=0$. We discuss the implications of these results for possible definitions of surface tensions in active fluids.

cond-mat.stat-mech↗

arXiv2023

Biases in Inverse Ising Estimates of Near-Critical Behaviour

Inverse Ising inference allows pairwise interactions of complex binary systems to be reconstructed from empirical correlations. Typical estimators used for this inference, such as Pseudo-likelihood maximization (PLM), are biased. Using the Sherrington-Kirkpatrick (SK) model as a benchmark, we show that these biases are large in critical regimes close to phase boundaries, and may alter the qualitative interpretation of the inferred model. In particular, we show that the small-sample bias causes models inferred through PLM to appear closer-to-criticality than one would expect from the data. Data-driven methods to correct this bias are explored and applied to a functional magnetic resonance imaging (fMRI) dataset from neuroscience. Our results indicate that additional care should be taken when attributing criticality to real-world datasets.

cond-mat.dis-nn↗

arXiv2022

Direct Imaging of Contacts and Forces in Colloidal Gels

Colloidal dispersions are prized as model systems to understand basic properties of materials, and are central to a wide range of industries from cosmetics to foods to agrichemicals. Among the key developments in using colloids to address challenges in condensed matter is to resolve the particle coordinates in 3D, allowing a level of analysis usually only possible in computer simulation. However in amorphous materials, relating mechanical properties to microscopic structure remains problematic. This makes it rather hard to understand, for example, mechanical failure. Here we address this challenge by studying the contacts and the forces between particles, as well as their positions. To do so, we use a colloidal model system (an emulsion) in which the interparticle forces and local stress can be linked to the microscopic structure. We demonstrate the potential of our method to reveal insights into the failure mechanisms of soft amorphous solids by determining local stress in a colloidal gel. In particular, we identify `force chains' of load-bearing droplets, and local stress anisotropy, and investigate their connection with locally rigid packings of the droplets.

cond-mat.soft↗

arXiv2021

Wetting transition of active Brownian particles on a thin membrane

We study non-equilibrium analogues of surface phase transitions in a minimal model of active particles in contact with a purely repulsive potential barrier that mimics a thin porous membrane. Under conditions of bulk motility-induced phase separation, the interaction strength $\varepsilon_w$ of the barrier controls the affinity of the dense phase for the barrier region. We uncover clear signatures of a wetting phase transition as $\varepsilon_w$ is varied. In common with its equilibrium counterpart, the character of this transition depends on the system dimensionality: a continuous transition with large density fluctuations and gas bubbles is uncovered in 2d while 3d systems exhibit a sharp transition absent of large correlations.

cond-mat.stat-mech↗

arXiv2021

Relaxation mechanisms in supercooled liquids past the Mode--Coupling Crossover: Cooperatively Re--arranging Regions vs Excitations

Among the challenges in discriminating between theoretical approaches to the glass transition is obtaining suitable data. In particular, particle--resolved data in liquids supercooled past the mode--coupling crossover has until recently been hard to obtain. Here we combine nano-particle resolved experiments and GPU simulation data which addresses this and investigate the predictions of differing theoretical approaches. We find support for both dynamic facilitation and thermodynamic approaches. In particular, excitations, the elementary units of relaxation in dynamic facilitation theory follow the predicted scaling behaviour and the properties of cooperatively rearranging regions (CRRs) are consistent with RFOT theory. At weak supercooling there is limited correlation between particles identified in excitations and CRRs, but this increases very substantially at deep supercooling. We identify a timescale related to the CRRs which is coupled to the structural relaxation time and thus decoupled from the excitation timescale, which remains microscopic.

cond-mat.soft↗

arXiv2020

Phase separation and multibody effects in three-dimensional active Brownian particles

Simulation studies of the phase diagram of repulsive active Brownian particles in three dimensions reveal that the region of motility-induced phase separation between a high and low density phase is enclosed by a region of gas-crystal phase separation. Near-critical loci and structural crossovers can additionally be identified in analogy with simple fluids. Motivated by the striking similarity to the behaviour of equilibrium fluids with short-ranged pair-wise attractions, we show that a direct mapping to pair potentials in the dilute limit implies interactions that are insufficiently attractive to engender phase separation. Instead, this is driven by the emergence of multi-body effects associated with particle caging that occurs at sufficiently high number density. We quantify these effects via information-theoretical measures of $n$-body effective interactions extracted from the configurational structure.

cond-mat.stat-mech↗

arXiv2020

Dynamical Phase Transitions and their Relation to Thermodynamic Glass Physics

We review recent developments in structural-dynamical phase transitions in trajectory space. An open question is how the dynamic facilitation theory of the glass transition may be reconciled with thermodynamic theories that posit a vanishing configurational entropy. Dynamic facilitation theory invokes a dynamical phase transition, between an active phase (close to the normal liquid) and an inactive phase which is glassy, whose order parameter is either dynamic or a time-averaged structural quantity. In particular, the dynamical phase transition in systems with non-trivial thermodynamics manifests signatures of a lower critical point, which lies close to the putative Kauzmann temperature, where any thermodynamic phase transition to an ideal glass state might occur. We discuss these findings, and suggest that the lower critical point of the structural-dynamical phase transition may be related to the large drop in configurational entropy that occurs in the inactive phase of the dynamical phase transition. Increasing supercooling thus brings configurational entropy of the normal liquid much lower, along with the temperature.

cond-mat.stat-mech↗

arXiv2019

The Devil is in the details: Pentagonal bipyramids and dynamic arrest

Colloidal suspensions have long been studied as a model for atomic and molecular systems, due to the ability to fluorescently label and individually track each particle, yielding particle-resolved structural information. This allows various local order parameters to be probed that are otherwise inaccessible for a comparable molecular system. For phase transitions such as crystallisation, appropriate order parameters which emphasise 6-fold symmetry are a natural choice, but for vitrification the choice of order parameter is less clear cut. Previous work has highlighted the importance of icosahedral local structure as the glass transition is approached. However, counting icosahedra or related motifs is not a continuous order parameter in the same way as, for example, the bond-orientational order parameters $Q_{6}$ and $W_6$. In this work we investigate the suitability of using pentagonal bipyramid membership, a structure which can be assembled into larger, five-fold symmetric structures, as a finer order parameter to investigate the glass transition. We explore various structural and dynamic properties and show that this new approach produces many of the same findings as simple icosahedral membership, but we also find that large instantaneous displacements are often correlated with significant changes in pentagonal bipyramid membership, and unlike the population of defective icosahedra, the pentagonal bypyramid membership and spindle number do not saturate for any measured volume fraction, but continues to increase.

cond-mat.soft↗

arXiv2019

Many-body correlations from integral geometry

In a recent letter we presented a framework for predicting the concentrations of many-particle local structures inside the bulk liquid as a route to assessing changes in the liquid approaching dynamical arrest. Central to this framework was the morphometric approach, a synthesis of integral geometry and liquid state theory, which has traditionally been derived from fundamental measure theory. We present the morphometric approach in a new context as a generalisation of scaled particle theory, and derive several morphometric theories for hard spheres of fundamental and practical interest. Our central result is a new theory which is particularly suited to the treatment of many-body correlation functions in the hard sphere liquid, which we demonstrate by numerical tests against simulation.

cond-mat.stat-mech↗

arXiv2019

Competing Active and Passive Interactions Drive Amoeba-like Living Crystallites and Ordered Bands

Swimmers and self-propelled particles are physical models for the collective behaviour and motility of a wide variety of living systems, such as bacteria colonies, bird flocks and fish schools. Such artificial active materials are amenable to physical models which reveal the microscopic mechanisms underlying the collective behaviour. Here we study colloids in a DC electric field. Our quasi-two-dimensional system of electrically-driven particles exhibits a rich and exotic phase behaviour. At low field strengths, electrohydrodynamic flows lead to self-organisation into crystallites with hexagonal order. Upon self-propulsion of the particles due to Quincke rotation, we find an ordered phase of active matter in which the motile crystallites constantly change shape and collide with one another. At higher field strengths, this "dissolves" to an active gas. We parameterise a particulate simulation model which reproduces the experimentally observed phases and, at higher field strengths predicts an activity-driven demixing to band-like structures.

cond-mat.soft↗

arXiv2019

Morphometric approach to many-body correlations in hard spheres

We model the thermodynamics of local structures within the hard sphere liquid at arbitrary volume fractions through the \textit{morphometric} calculation of $n$-body correlations. We calculate absolute free energies of local geometric motifs in excellent quantitative agreement with molecular dynamics simulations across the liquid and supercooled liquid regimes. We find a bimodality in the density library of states where five-fold symmetric structures appear lower in free energy than four-fold symmetric structures, and from a single reaction path predict a relaxation barrier which scales linearly in the compressibility factor. The method provides a new route to assess changes in the free energy landscape at volume fractions dynamically inaccessible to conventional techniques.

cond-mat.stat-mech↗

arXiv2018

Dynamical solid-liquid transition through oscillatory shear

Starting from an ideal crystalline state, we numerically study a nonequilibrium dynamical order- disorder transition promoted by the application of a periodic shearing protocol at low temperatures in model systems in two and three dimensions. We observe a continuous (2D) and discontinuous (3D) dynamical transition from an ordered to a disordered steady state. Through the analysis of large-scale simulations, we show that the amorphization mechanism around the discontinuous transition is reminiscent of spinodal decomposition.

cond-mat.soft↗

arXiv2018

Coupling of sedimentation and liquid structure: influence on hard sphere nucleation

The discrepancy in nucleation rate densities between simulated and experimental hard spheres remains staggering and unexplained. Suggestively, more strongly sedimenting colloidal suspensions of hard spheres nucleate much faster than weakly sedimenting systems. In this work we consider firstly the effect of sedimentation on the structure of colloidal hard spheres, by tuning the density mismatch between solvent and colloidal particles. In particular we investigate the effect on the degree of five fold symmetry present. Secondly we study the size of density fluctuations in these experimental systems in comparison to simulations. The density fluctuations are measured by assigning each particle a local density, which is related to the number of particles within a distance of 3.25 particle diameters. The standard deviation of these local densities gives an indication of the fluctuations present in the system. Five fold symmetry is suppressed by a factor of two when sedimentation is induced in our system. Density fluctuations are also increased by a factor of two in experiments compared to simulations. The change in five fold symmetry makes a difference to the expected nucleation rates, but we demonstrate that it is ultimately too small to resolve the discrepancy between experiment and simulation, while the fluctuations are shown to be an artefact of 3d particle tracking.

cond-mat.soft↗

arXiv2018

The race to the bottom: approaching the ideal glass?

Key to resolving the scientific challenge of the glass transition is to understand the origin of the massive increase in viscosity of liquids cooled below their melting temperature (avoiding crystallisation). A number of competing and often mutually exclusive theoretical approaches have been advanced to describe this phenomenon. Some posit a bona fide thermodynamic phase to an "ideal glass", an amorphous state with exceptionally low entropy. Other approaches are built around the concept of the glass transition as a primarily dynamic phenomenon. These fundamentally different interpretations give equally good descriptions of the data available, so it is hard to determine which -- if any -- is correct. Recently however this situation has begun to change. A consensus has emerged that one powerful means to resolve this longstanding question is to approach the putative thermodynamic transition sufficiently closely, and a number of techniques have emerged to meet this challenge. Here we review the results of some of these new techniques and discuss the implications for the existence -- or otherwise -- of the thermodynamic transition to an ideal glass.

cond-mat.soft↗

arXiv2018

Devitrification of the Kob-Andersen glass former: Competition with the locally favored structure

Supercooled liquids are kinetically trapped materials in which the transition to a thermodynamically more stable state with long-range order is strongly suppressed. To assess the glass-forming abilities of a liquid empirical rules exist, but a comprehensive microscopic picture of devitrification is still missing. Here we study the crystallization of a popular model glass former, the binary Kob-Andersen mixture, in small systems. We perform trajectory sampling employing the population of the locally favored structure as order parameter. While for large population a dynamical phase transition has been reported, here we show that biasing towards a small population of locally favored structures induces crystallization, and we estimate the free energy difference. This result sheds new light on the competition between local and global structure in glass-forming liquids and its implications for crystallization.

cond-mat.stat-mech↗