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Alessandro Patti

Publications and source records attributed to Alessandro Patti.

27 records · Page 2Linked to original sources

Is Fickian Yet Non-Gaussian Diffusion Ubiquitous?

Recent studies unveiled the Fickian yet non-Gaussian (FNG) dynamics of many soft matter systems and suggested this phenomenon as a general characteristic of the diffusion in complex fluids. In particular, it was shown that the distribution of particle displacements in Fickian diffusion is not necessarily Gaussian, and thus the Einstein and Smoluchowski theory describing the Brownian motion of individual objects in a fluid would not be applicable. In this Letter, we investigate whether the FNG dynamics so far reported in gels, granular materials, biological and active matter systems, is also a distinctive feature of colloidal liquid crystals. To this end, we perform Brownian Dynamics simulations of oblate and prolate colloidal particles in the nematic phase. We detect a normal and Gaussian dynamics at short and long time scales, whereas, at intermediate time scales, a non-Fickian and non-Gaussian dynamics is found. Additionally, we revisit the nature of the decay of the self-van Hove correlation function, $G_s(r,t)$, which is here approximated with an ellipsoidal, rather than spherical, Gaussian distribution. The new expression that we propose is able to correctly assess the Gaussian dynamics in inherently anisotropic systems, like liquid crystals, where the standard Gaussian approximation of $G_s(r,t)$ would fail.

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Transferable Coarse-Grained Model for Methacrylate-Based Copolymers

A versatile and transferable coarse-grained (CG) model was developed to investigate the self-assembly of two ubiquitous methacrylate-based copolymers: poly(ethylene oxide-b-methylmethacrylate) (PEO-b-PMMA) and poly(ethylene oxide-b-butylmethacrylate) (PEO-b-PBMA). We derive effective CG potentials that can reproduce their behaviour in aqueous and organic polymer solutions, pure copolymer systems, and at the air-water interface following a hybrid structural-thermodynamic approach, which incorporates macroscopic and atomistic-level information. The parameterization of the intramolecular CG potentials results from matching the average probability distributions of bonded degrees of freedom for chains in solution and in pure polymer systems with those obtained from atomistic simulations. Potential energy functions for the description of effective intra- and intermolecular interactions are elected to be fully compatible with the MARTINI force-field. The optimized models allow for an accurate prediction of the structural properties of a number of methacrylate-based copolymers of different length and at different thermodynamic state points. In addition, we propose a single-segment model for tetrahydrofuran (THF), an organic solvent commonly used in methacrylate-based polymer processing. This model exhibits a fluid phase behaviour qualitatively close to that predicted by more sophisticated molecular models and can reproduce the experimental free energy of transfer between water and octanol.

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Dynamic Monte Carlo algorithm for out-of-equilibrium processes in colloidal dispersions

Colloids have a striking relevance in a wide spectrum of industrial formulations, spanning from personal care products to protective paints. Their behaviour can be easily influenced by extremely weak forces, which disturb their thermodynamic equilibrium and dramatically determine their performance. Motivated by the impact of colloidal dispersions in fundamental science and formulation engineering, we have designed an efficient Dynamic Monte Carlo (DMC) approach to mimic their out-of-equilibrium dynamics. Our recent theory, which provided a rigorous method to reproduce the Brownian motion of colloids by MC simulations, is here generalised to reproduce the Brownian motion of colloidal particles during transitory unsteady states, when their thermodynamic equilibrium is significantly modified. To this end, we investigate monodisperse and bidisperse rod-like particles in the isotropic phase and apply an external field that forces their reorientation along a common direction and induces an isotropic-to-nematic phase transition. We also study the behaviour of the system once the external field is removed. Our simulations are in excellent quantitative agreement with Brownian Dynamics simulations when the DMC results are rescaled with a time-dependent acceptance ratio, which depends on the strength of the applied field. Further generalising our DMC algorithm to processes displaying significant density fluctuations, such as nucleation and growth, where the MC acceptance ratio is expected to depend on both time and space, is currently under investigation.

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Monte Carlo simulation of binary mixtures of hard colloidal cuboids

We perform extensive Monte Carlo simulations to investigate the phase behaviour of colloidal suspensions of hard board-like particles (HBPs). While theories restricting particle orientation or ignoring higher ordered phases suggest the existence of a stable biaxial nematic phase, our recent simulation results on monodisperse systems indicate that this is not necessarily the case, even for particle shapes exactly in between prolate and oblate geometries, usually referred to as self-dual shape. Motivated by the potentially striking impact of incorporating biaxial ordering into display applications, we extend our investigation to bidisperse mixtures of short and long HBPs and analyse whether size dispersity can further enrich the phase behaviour of HBPs, eventually destabilise positionally ordered phases and thus favour the formation of the biaxial nematic phase. Not only do our results indicate that bidisperse mixtures of self-dual shaped HBPs cannot self-assemble into biaxial nematic phases, but they also show that these particles are not able to form uniaxial nematic phases either. This surprising behaviour is also observed in monodisperse systems. Additionally, bidisperse HBPs tend to phase separate in coexisting isotropic and smectic phases or, at relatively large pressures, in a smectic phase of mostly short HBPs and a smectic phase of mostly long HBPs. We conclude that limiting the particle orientational degrees of freedom or neglecting the presence of positionally ordered (smectic, columnar and crystal) phases can dramatically alter the phase behaviour of HBPs and unrealistically enlarge the region of stability of the biaxial nematic phase.

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Frustration of the isotropic-columnar phase transition of colloidal hard platelets by a transient cubatic phase

Using simulations and theory, we show that the cubatic phase is metastable for three model hard platelets. The locally favored structures of perpendicular particle stacks in the fluid prevent the formation of the columnar phase through geometric frustration resulting in vitrification. Also, we find a direct link between structure and dynamic heterogeneities in the cooperative rotation of particle stacks, which is crucial for the devitrification process. Finally, we show that the life time of the glassy cubatic phase can be tuned by surprisingly small differences in particle shape.

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Heterogeneous Dynamics in Columnar Liquid Crystals of Parallel Hard Rods

In the wake of previous studies on the rattling-and-jumping diffusion in smectic liquid crystal phases of colloidal rods, we analyze here for the first time the heterogeneous dynamics in columnar phases. More specifically, we perform computer simulations to investigate the relaxation dynamics of a binary mixture of perfectly aligned hard spherocylinders. We detect that the columnar arrangement of the system produces free-energy barriers the particles should overcome to jump from one column to another, thus determining a hopping-type diffusion. This phenomenon accounts for the non-Gaussian inter-column diffusion and shows a two-step structural relaxation which is remarkably analogous to that of out-of-equilibrium glass-forming systems and gels. Surprisingly enough, slight deviations from the behavior of simple liquids due to transient cages is also observed in the direction perpendicular to this plane, where the system is usually referred to as liquid-like.

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Molecular Modeling of Self-assembling Hybrid Materials (PhD Thesis)

Lattice Monte Carlo simulations are used to study the phase behavior of self-assembling ordered mesoporous materials formed by an organic template with amphiphilic properties and an inorganic precursor in a model solvent. Three classes of inorganic precursors have been modeled: terminal (R-Si-(OEt)3) and bridging ((EtO)3-Si-R-Si-(OEt)3)) organosilica precursors (OSPs), along with pure silica precursors (Si-(OEt)4). Each class has been studied by analyzing its solubility in the solvent and the solvophobicity of the inorganic group. At high surfactant concentrations, periodic ordered structures, such as hexagonally-ordered cylinders or lamellas, can be obtained depending on the OSPs used. Ordered structures were obtained in a wider range of conditions when bridging hydrophilic OSPs have been used, because a higher surfactant concentration was reached in the phase where the material was formed. Terminal and bridging OSPs produced ordered structures only when the organic group is solvophilic. In this case, a partial solubility between the precursor and the solvent or a lower temperature favored the formation of ordered phases. With particular interest, we have analyzed the range of conditions leaving to the formation of cylindrical structures, which have been evaluated according to the pore size distribution, the pore wall thickness, the distribution and the accessibility of the functional organic groups around the pores. The phase behavior has been also evaluated by applying the quasi-chemical theory, which cannot predict the formation of ordered structures, but confirmed the results of simulations when no ordered structures were observed. The study of the phase and aggregation behavior of two different surfactants, one modeled by a linear chain of head segments and the other modeled by a branched-head, permitted us to evaluate some structural differences of the materials obtained.

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Collective Diffusion of Colloidal Hard Rods in Smectic Liquid Crystals: Effect of Particle Anisotropy

We study the layer-to-layer diffusion in smectic-A liquid crystals of colloidal hard rods with different length-to-diameter ratios using computer simulations. The layered arrangement of the smectic phase yields a hopping-type diffusion due to the presence of permanent barriers and transient cages. Remarkably, we detect stringlike clusters composed of inter-layer rods moving cooperatively along the nematic director. Furthermore, we find that the structural relaxation in equilibrium smectic phases shows interesting similarities with that of out-of-equilibrium supercooled liquids, although there the particles are kinetically trapped in transient rather than permanent cages. Additionally, at fixed packing fraction we find that the barrier height increases with increasing particle anisotropy, and hence the dynamics is more heterogeneous and non-Gaussian for longer rods, yielding a lower diffusion coefficient along the nematic director and smaller clusters of inter-layer particles that move less cooperatively. At fixed barrier height, the dynamics becomes more non-Gaussian and heterogeneous for longer rods that move more collectively giving rise to a higher diffusion coefficient along the nematic director.

cond-mat.soft↗

Non-Gaussian Dynamics in Smectic Liquid Crystals of Parallel Hard Rods

Using computer simulations, we studied the diffusion and structural relaxation in equilibrium smectic liquid crystal bulk phases of parallel hard spherocylinders. These systems exhibit a non-Gaussian layer-to-layer diffusion due to the presence of periodic barriers and transient cages, and show remarkable similarities with the behavior of out-of-equilibrium supercooled liquids. We detect a very slow inter-layer relaxation dynamics over the whole density range of the stable smectic phase which spans a time interval of four time decades. The intrinsic nature of the layered structure yields a hopping-type diffusion which becomes more heterogeneous for higher packing fractions. In contrast, the in-layer dynamics is typical of a dense fluid with a relatively fast decay. Our results on the dynamic behavior agree well with that observed in systems of freely rotating hard rods, but differ quantitavely, as the height of the periodic barriers reduces to zero at the nematic-smectic transition for aligned rods, while it remains finite for freely rotating rods.

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