arXiv subjects

Alessio Zaccone

Publications and source records attributed to Alessio Zaccone.

At least 163 records · Page 9Linked to original sources

arXiv2016

Chain-Assisted Charge Transport in Semicrystalline Conjugated Polymers

Charge-carrier transport in a paradigmatic semicrystalline polymer semiconductor (P3HT) is important for both fundamental understanding and applications. In samples with enhanced structural disorder due to ad-hoc point defects, the mobility displays rich behavior as a function of electric field (F) and temperature (T). At low T, the mobility increases with the applied field, but upon further increasing T, the field-dependence becomes shallower. Eventually, at the highest T considered, the slope changes sign and the mobility then decreases with the field. This phenomenon can be interpreted with our model as a result of the competition between intrachain conductive-like transport (which slows on increasing F) and interchain activated transport (which is faster at higher F). The former is controlling at high T where interchain hops are strictly limited to nearest-neighbor monomers on adjacent chains. At low T, instead, interchain hops to distant sites are allowed and control the positive correlation of the mobility with the field.

cond-mat.soft↗

arXiv2016

Polymer glass transition occurs at the marginal rigidity point with connectivity z*=4

We re-examine the physical origin of the polymer glass transition from the point of view of marginal rigidity, which is achieved above a certain number of intermolecular contacts. In the case of polymer chains in a melt / poor solvent, each monomer has two neighbors bound by covalent bonds and also a number of central-force contacts modelled by the Lennard-Jones (LJ) potential. We find that when the average number of contacts per monomer (covalent and non-covalent) exceeds the critical value z*=4, the system becomes solid and the dynamics arrested - a state that we declare the glass. Coarse-grained Brownian dynamics simulations show that at sufficient strength of LJ attraction (which effectively represents the depth of quenching, or the quality of solvent) the polymer globule indeed crosses the threshold of z*=4, and does become a glass. We verify this by showing the distinction between the `liquid' polymer droplet at z z*, which retains its shape frozen at the moment of z* crossover. These results provide a robust working criterion to tell the liquid apart from the glass for the linear polymers.

cond-mat.soft↗

arXiv2015

Interatomic repulsion softness directly controls the fragility of supercooled metallic melts

We present an analytic scheme to connect the fragility and viscoelasticity of metallic glasses to the effective ion-ion interaction in the metal. This is achieved by an approximation of the short-range repulsive part of the interaction, combined with nonaffine lattice dynamics to obtain analytical expressions for the shear modulus, viscosity, and fragility in terms of the ion-ion interaction. By fitting the theoretical model to experimental data, we are able to link the steepness of the interionic repulsion to the Thomas-Fermi screened Coulomb repulsion and to the Born-Mayer valence-electron overlap repulsion for various alloys. The result is a simple closed-form expression for the fragility of the supercooled liquid metal in terms of few crucial atomic-scale interaction and anharmonicity parameters. In particular, a linear relationship is found between the fragility and the energy scales of both the screened Coulomb and the electron-overlap repulsions. This relationship opens up opportunities to fabricate alloys with tailored thermo-elasticity and fragility by rationally tuning the chemical composition of the alloy according to general principles. The analysis presented here brings a new way of looking at the link between the outer-shell electronic structure of metals and metalloids and the viscoelasticity and fragility thereof.

cond-mat.soft↗

arXiv2015

Microscopic Origin of the Hofmeister Effect in Gelation Kinetics of Colloidal Silica

The gelation kinetics of silica nanoparticles is a central process in physical chemistry, yet it is not fully understood. Gelation times are measured to increase by over 4 orders of magnitude, simply changing the monovalent salt species from CsCl to LiCl. This striking effect has no microscopic explanation within current paradigms. The trend is consistent with the Hofmeister series, pointing to short-ranged solvation effects not included in the standard colloidal (DLVO) interaction potential. By implementing a simple form for short-range repulsion within a model that relates the gelation timescale to the colloidal interaction forces, we are able to explain the many orders of magnitude difference in the gelation times at fixed salt concentration. The model allows us to estimate the magnitude of the non-DLVO hydration forces, which dominate the interparticle interactions on the length scale of the hydrated ion diameter. This opens the possibility of finely tuning the gelation time scale of nanoparticles by just adjusting the background electrolyte species

cond-mat.soft↗

arXiv2013

Ratcheted diffusion transport through crowded nanochannels

The problem of transport through nanochannels is one of the major questions in cell biology, with a wide range of applications. Brownian ratchets are fundamental in various biochemical processes, and are roughly divided into two categories: active (usually ATP-powered) molecular motors and passive constructions with a directional bias, where the transport is driven by thermal motion. In this paper we discuss the latter process, of spontaneous translocation of molecules (Brownian particles) by ratcheted diffusion with no external energy input: a problem relevant for protein translocation along bacterial flagella or injectosome complex, or DNA translocation by bacteriophages. We use molecular dynamics simulations and statistical theory to identify two regimes of transport: at low rate of particles injection into the channel the process is controlled by the individual diffusion towards the open end (the first passage problem), while at a higher rate of injection the crowded regime sets in. In this regime the particle density in the channel reaches a constant saturation level and the resistance force increases substantially, due to the osmotic pressure build-up. To achieve a steady-state transport, the apparatus that injects new particles into a crowded channel has to operate with an increasing power consumption, proportional to the length of the channel and the required rate of transport. The analysis of resistance force, and accordingly -- the power required to inject the particles into a crowded channel to oversome its clogging, is also relevant for many microfluidics applications.

cond-mat.soft↗

arXiv2013

Colloidal gelation with variable attraction energy

We present an approximation scheme to the master kinetic equations for aggregation and gelation with thermal breakup in colloidal systems with variable attraction energy. With the cluster fractal dimension $d_{f}$ as the only phenomenological parameter, rich physical behavior is predicted. The viscosity, the gelation time and the cluster size are predicted in closed form analytically as a function of time, initial volume fraction and attraction energy by combining the reversible clustering kinetics with an approximate hydrodynamic model. The fractal dimension $d_{f}$ modulates the time evolution of cluster size, lag time and gelation time and of the viscosity. The gelation transition is strongly nonequilibrium and time-dependent in the unstable region of the state diagram of colloids where the association rate is larger than the dissociation rate. Only upon approaching conditions where the initial association and the dissociation rates are comparable for all species (which is a condition for the detailed balance to be satisfied) aggregation can occur with $d_{f}=3$. In this limit, homogeneous nucleation followed by Lifshitz-Slyozov coarsening is recovered. In this limited region of the state diagram the macroscopic gelation process is likely to be driven by large spontaneous fluctuations associated with spinodal decomposition.

cond-mat.soft↗

arXiv2013

Electrostatics controls the formation of amyloid-like superstructures in protein aggregation

The possibility for proteins to aggregate in different superstructures, i.e. large-scale polymorphism, has been widely observed, but an understanding of the physico-chemical mechanisms behind it is still out of reach. Here we present a theoretical model for the description of a generic aggregate formed from an ensemble of charged proteins. The model predicts the formation of multi-fractal structures with the geometry of the growth determined by the electrostatic interactions between single proteins. The model predictions are successfully verified in comparison with experimental curves for aggregate growth. The model is general and is able to predict aggregate morphologies occurring both in vivo and in vitro. Our findings provide for the first time a unifying and general framework where the physical interactions between single proteins, the aggregate morphology and the growth kinetics are connected into a single model in excellent agreement with the experimental data.

physics.bio-ph↗

arXiv2013

Unexpected decoupling of stretching and bending modes in protein gels

We show that gels formed by arrested spinodal decomposition of protein solutions exhibit elastic properties in two distinct frequency domains, both elastic moduli exhibiting a remarkably strong dependence on volume fraction. Considering the large difference between the protein size and the characteristic length of the network we model the gels as porous media and show that the high and low frequency elastic moduli can be respectively attributed to stretching and bending modes. The unexpected decoupling of the two modes in the frequency domain is attributed to the length scale involved: while stretching mainly relates to the relative displacement of two particles, bending involves the deformation of a strand with a thickness of the order of a thousand particle diameters.

cond-mat.soft↗

arXiv2012

Disorder-assisted melting and the glass transition in amorphous solids

The mechanical response of solids depends on temperature because the way atoms and molecules respond collectively to deformation is affected at various levels by thermal motion. This is a fundamental problem of solid state science and plays a crucial role in metallurgy, aerospace engineering, energy. In glasses the vanishing of rigidity upon increasing temperature is the reverse process of the glass transition. It remains poorly understood due to the disorder leading to nontrivial (nonaffine) components in the atomic displacements. Our theory explains the basic mechanism of the melting transition of amorphous (disordered) solids in terms of the lattice energy lost to this nonaffine motion, compared to which thermal vibrations turn out to play only a negligible role. It predicts the square-root vanishing of the shear modulus $G\sim\sqrt{T_{c}-T}$ at criticality observed in the most recent numerical simulation study. The theory is also in good agreement with classic data on melting of amorphous polymers (for which no alternative theory can be found in the literature) and offers new opportunities in materials science.

cond-mat.soft↗

arXiv2012

Theory of molecular crowding in Brownian hard-sphere liquids with application to the polymer coil-globule transition

We derive an analytical pair potential of mean force for Brownian molecules in the liquid-state. Our approach accounts for many-particle correlations of crowding particles of the liquid, and for diffusive transport across the spatially modulated local density of crowders in the dense environment. Specializing on the limit of equal-size particles, we show that this diffusive transport leads to additional density- and structure-dependent terms in the interaction potential, and to a much stronger attraction (by a factor ~4 at average volume fraction of crowders 0.25) than in the standard depletion interaction where the diffusive effects are neglected. As an illustration of the theory, we use it to study the size of a polymer chain in a solution of inert crowders. Even in the case of athermal background solvent, when a classical chain should be fully swollen, we find a sharp coil-globule transition of the ideal chain collapsing at a critical value of the crowder volume fraction ~0.145.

cond-mat.soft↗

arXiv2012

Kramers rate theory of ionization and dissociation of bound states

Calculating the microscopic dissociation rate of a bound state, such as a classical diatomic molecule, has been difficult so far. The problem was that standard theories require an energy barrier over which the bound particle (or state) escapes into the preferred low-energy state. This is not the case when the long-range repulsion responsible for the barrier is either absent or screened (as in Cooper pairs, ionized plasma, or biomolecular complexes). We solve this classical problem by accounting for entropic memory at the microscopic level. The theory predicts dissociation rates for arbitrary potentials and is successfully tested on the example of plasma, where it yields an estimate of ionization in the core of Sun in excellent agreement with experiments. In biology, the new theory accounts for crowding in receptor-ligand kinetics and protein aggregation.

cond-mat.stat-mech↗

arXiv2012

Network disorder and nonaffine deformations in marginal solids

The most profound effect of disorder on the elastic response of solids is the nonaffinity of local displacements whereby the atoms (particles, network junctions) do not simply follow the macroscopic strain, as they do in perfect crystals, but undergo additional displacements which result in a softening of response. Whether disorder can produce further effects has been an open and difficult question due to our poor understanding of nonaffinity. Here we present a systematic analysis of this problem by allowing both network disorder and lattice coordination to vary continuously under account of nonaffinity. In one of its limits, our theory, supported by numerical simulations, shows that in lattices close to the limit of mechanical stability the elastic response stiffens proportionally to the degree of disorder. This result has important implications in a variety of areas: from understanding the glass transition problem to the mechanics of biological networks such as the cytoskeleton.

cond-mat.soft↗

arXiv2011

Quantifying the Reversible Association of Thermosensitive Nanoparticles

Under many conditions, biomolecules and nanoparticles associate by means of attractive bonds, due to hydrophobic attraction. Extracting the microscopic association or dissociation rates from experimental data is complicated by the dissociation events and by the sensitivity of the binding force to temperature (T). Here we introduce a theoretical model that combined with light-scattering experiments allows us to quantify these rates and the reversible binding energy as a function of T. We apply this method to the reversible aggregation of thermoresponsive polystyrene/poly(N-isopropylacrylamide) core-shell nanoparticles, as a model system for biomolecules. We find that the binding energy changes sharply with T, and relate this remarkable switchable behavior to the hydrophobic-hydrophilic transition of the thermosensitive nanoparticles.

cond-mat.soft↗

arXiv2011

Approximate analytical description of the nonaffine response of amorphous solids

An approximation scheme for model disordered solids is proposed that leads to the fully analytical evaluation of the elastic constants under explicit account of the inhomogeneity (nonaffinity) of the atomic displacements. The theory is in quantitative agreement with simulations for central-force systems and predicts the vanishing of the shear modulus at the isostatic point with the linear law μ ~ (z - 2d), where z is the coordination number. The vanishing of rigidity at the isostatic point is shown to be a consequence of the canceling out of positive affine and negative nonaffine terms.

cond-mat.soft↗

arXiv2011

Shear-driven solidification of dilute colloidal suspensions

We show that the shear-induced solidification of dilute charge-stabilized (DLVO) colloids is due to the interplay between the shear-induced formation and breakage of large non-Brownian clusters. While their size is limited by breakage, their number density increases with the shearing-time. Upon flow cessation, the dense packing of clusters interconnects into a rigid state by means of grainy bonds, each involving a large number of primary colloidal bonds. The emerging picture of shear-driven solidification in dilute colloidal suspensions combines the gelation of Brownian systems with the jamming of athermal systems.

cond-mat.soft↗

arXiv2010

On a Coarse-Graining Concept in Colloidal Physics with Application to Fluid and Arrested Colloidal Suspensions in Shearing Fields

We poorly understand the macroscopic properties of complex fluids and of amorphous bodies in general. This is mainly due to the interplay between phenomena at different levels and length-scales. In particular, it is not necessarily true that the microscopic level (dominated by direct interactions) coincides with the level where the continuum description comes into play. This is typically the case in the presence of structural inhomogeneities which are inherent to all structurally disordered states of matter below close packing. As a consequence, the macroscopic response to external fields of either fluid or arrested disordered states is not well understood. In order to disentangle this complexity, in this work we build upon a simple yet seemingly powerful concept. This can be summarized as follows: the mesoscopic length-scale of structural inhomogeneities is assumed to be the characteristic length-scale of the effective building blocks, while the degrees of freedom of the primary particles are integrated out. Theoretical results are derived, in the present work, for the macroscopic response of fluid and dynamically arrested model colloidal states in fields of shear. The predictions of the coarse-grained theories and the applicability of the principle are tested in comparison with original simulation and experimental data.

cond-mat.soft↗

arXiv2010

Shear-induced reaction-limited aggregation kinetics of Brownian particles at arbitrary concentrations

The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the range considered. By generalizing Kramers' rate theory to the presence of collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

cond-mat.soft↗

arXiv2010

Theory of activated-rate processes under shear with application to shear-induced aggregation of colloids

Using a novel approximation scheme within the convective diffusion (two body Smoluchowski) equation framework, we unveil the shear-driven aggregation mechanism at the origin of structure-formation in sheared colloidal systems. The theory, verified against numerics and experiments, explains the induction time followed by explosive (irreversible) rise of viscosity observed in charge-stabilized colloidal and protein systems under steady shear. The Arrhenius-type equation with shear derived here, extending Kramers theory in the presence of shear, is the first analytical result clearly showing the important role of shear-drive in activated-rate processes as they are encountered in soft condensed matter.

cond-mat.soft↗