arXiv subjects

Henricus H. Wensink

Publications and source records attributed to Henricus H. Wensink.

15 recordsLinked to original sources

arXiv2025

Spontaneous Chiral Symmetry Breaking in Polydisperse Achiral Near-Rigid Nematogens

Understanding chirality transfer from the molecular to the macroscopic scale poses a significant challenge in soft and biological condensed matter physics. Many nanorods of biological origin not only have chiral molecular features but also exhibit a spread in contour length leading to considerable size dispersity. On top of this, random backbone fluctuations are ubiquitous for non-rigid particles but their role in chirality transfer remains difficult to disentangle from that of their native chirality imparted by their effective shape or surface architecture. We report spontaneous entropy-driven chiral symmetry breaking from molecular simulations of cholesteric liquid-crystals formed from achiral bead-spring rods with a continuous spread in contour length and marginal chain bending. The symmetry-breaking is caused by long-lived chiral conformations of long rods undergoing chiral synchronization leading to a homochiral twisted nematic. A simple theory demonstrates that even without chiral synchronization, the presence of shape-persistent configurational fluctuations along with length-dispersity can be harnessed to generate non-zero chirality at moderate polydispersity.

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arXiv2025

Freezing in flat monolayers of soft spherocylinders

Lamellar or smectic phases often have an intricate intralamellar structure that remains scarcely understood from a microscopic viewpoint. In this work, we use molecular dynamics simulations to study the effect of volume exclusion and electrostatic repulsion on the phase transitions of a flat membrane of soft spherocylinders. With increasing rod packing, we identify nematic and solid phases and find that the nematic-crystal phase transition happens at a uniform packing fraction ($η_c \approx 0.82$), independent of the spherocylinder aspect ratio. This value is considerably higher than the well-known critical freezing transition of a hard disk fluid ($η_c \approx 0.7$) to which one could naively map a system of near-parallel rods with co-planar mass centers. We attribute this difference to a non-vanishing residual orientational entropy per rod. Our findings are corroborated by a simple theory based on a simple microscopic density functional theory of freezing of a two-dimensional rod fluid. Introduction of electrostatic interactions between the rods reduces the lateral compressibility of the monolayer fluid but keeps the positional order unhindered, which in turn maintains the packing fraction at the nematic-crystal transition. The strength of the orientational fluctuations of the individual rods in our membranes exhibits a density scaling that differs from 3D bulk smectics. Our findings contribute to a qualitative understanding of liquid crystal phase stability in strong planar confinement and engage with recent experimental explorations involving nanorods on 2D substrates.

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arXiv2024

Complex Smectic Phases in Polymer Grafted Shape-Uniform Cellulose Nano-Crystals

The effect of short chain grafting on the liquid crystalline (LC) ordering of nano-crystals is investigated using molecular dynamics simulations of a coarse-grained grafted nano-rod model. Monodisperse nano-rods, with aspect ratios typical of cellulose nano-crystals (CNCs) are grafted randomly with oligomers at different grafting densities. LC ordering depends non-trivially on grafting density as the effective nano-rod shape and softness is modified. Ungrafted rods exhibit Nematic and tilted Smectic-C phases. At 25\% grafting, the addition of a few side chains entirely suppresses Smectic order and instead a persistent Nematic phase is favoured. Intermediary grafting, around 50\%, results in a Nematic and the reappearance of tilted Smectic-F phases. Heavier grafting facilitates direct transitions to either Smectic-I with extreme tilt (75\%) or an un-tilted Smectic-B (100\%). Such behaviour falls outside of current hard or soft-rod descriptions of phase-transitions in rod-like LC systems and points to undiscovered LC behaviour in both shape-purified grafted/un-grafted CNCs.

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arXiv2023

Unavoidable emergent biaxiality in chiral molecular-colloidal hybrid liquid crystals

Chiral nematic or cholesteric liquid crystals (LCs) are mesophases with long-ranged orientational order featuring a quasi-layered periodicity imparted by a helical configuration but lacking positional order. Doping molecular cholesteric LCs with thin colloidal rods with a large length-to-width ratio or disks with a large diameter-to-thickness ratio adds another level of complexity to the system because of the interplay between weak surface boundary conditions and bulk-based elastic distortions around the particle-LC interface. By using colloidal disks and rods with different geometric shapes and boundary conditions, we demonstrate that these anisotropic colloidal inclusions exhibit biaxial orientational probability distributions, where they tend to orient with the long rod axes and disk normals perpendicular to the helix axis, thus imparting strong local biaxiality on the hybrid cholesteric LC structure. Unlike the situation in achiral hybrid molecular-colloidal LCs, where biaxial order emerges only at modest to high volume fractions of the anisotropic colloidal particles, the orientational probability distribution of colloidal inclusions immersed in chiral nematic hosts are unavoidably biaxial even at vanishingly low particle volume fractions. In addition, the colloidal inclusions induce local biaxiality in the molecular orientational order of the LC host medium, which enhances the weak biaxiality of the LC in a chiral nematic phase coming from the symmetry breaking caused by the presence of the helical axis. With analytical modeling and computer simulations based on minimizing the Landau de Gennes free energy of the host LC around the colloidals, we explain our experimental findings and conclude that the biaxial order of chiral molecular-colloidal LCs is strongly enhanced as compared to both achiral molecular-colloidal LCs and molecular cholesteric LCs and is rather unavoidable.

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arXiv2021

Second-virial theory for shape-persistent living polymers templated by discs

Living polymers composed of non-covalently bonded building blocks with weak backbone flexibility may self-assemble into thermoresponsive lyotropic liquid crystals. We demonstrate that the reversible polymer assembly and phase behavior can be controlled by the addition of (non-adsorbing) rigid colloidal discs which act as an entropic reorienting ``template" onto the supramolecular polymers. Using a particle-based second-virial theory that correlates the various entropies associated with the polymers and discs, we demonstrate that small fractions of discotic additives promote the formation of a polymer nematic phase. At larger disc concentrations, however, the phase is disrupted by collective disc alignment in favor of a discotic nematic fluid in which the polymers are dispersed anti-nematically. We show that the anti-nematic arrangement of the polymers generates a non-exponential molecular-weight distribution and stimulates the formation of oligomeric species. At sufficient concentrations the discs facilitate a liquid-liquid phase separation which can be brought into simultaneously coexistence with the two fractionated nematic phases, providing evidence for a four-fluid coexistence in reversible shape-dissimilar hard-core mixtures without cohesive interparticle forces. We stipulate the conditions under which such a phenomenon could be found in experiment.

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arXiv2020

Rotational and translational dynamics in dense fluids of patchy particles

We explore the effect of directionality on rotational and translational relaxation in glassy systems of patchy particles. Using molecular dynamics simulations we analyze the impact of two distinct patch geometries, one that enhance local icosahedral structure and one which does not strongly affect local order. We find that in nearly all investigated cases, rotational relaxation takes place on a much faster time scale than translational relaxation. By comparing to a simplified dynamical Monte Carlo model, we illustrate that rotational diffusion can be qualitatively explained as purely local motion within a fixed environment, which is not coupled strongly to the cage-breaking dynamics required for translational relaxation. Nonetheless, icosahedral patch placement has a profound effect on the local structure of the system, resulting in a dramatic slowdown at low temperatures which is strongest at an intermediate "optimal" patch size.

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arXiv2019

Tetrahedrality dictates dynamics in hard spheres

Glasses are ubiquitous amorphous solids that remain one of the big mysteries in condensed matter. Despite the vast body of literature on glasses, a unifying approach to link the structure and dynamics of glasses is still missing. A growing set of evidence, however, indicates the microscopic local geometry as a key ingredient. This originated from the seminal work of Frank, who conjectured that glasses may be the result of the local tendency of liquids to form icosahedral structures, which are not capable of globally filling space regularly. Here, we show that, for a fundamental glass model, dynamics can be fully understood by simply counting the number of tetrahedra. Both globally and locally, these local structures directly predict dynamical slowdown. After more than 60 years of Frank's Conjecture, it might not be the icosahedra that matter for glasses, but rather the tetrahedra inside them.

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arXiv2019

Designing slower glasses by manipulating their local structure

Glasses remain an elusive and poorly understood state of matter. For example, it is not clear how we can design an efficient macroscopic glass former by tuning the properties of its microscopic building blocks. In this paper, we propose a simple directional colloidal model that reinforces the optimal icosahedral local structure of binary hard-sphere glasses. We show that only this specific symmetry results in a dramatic slowing down of the dynamics. Our results open the door to controlling the dynamics of dense glassy systems by selectively promoting specific local structural environments.

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arXiv2018

Long-time anomalous swimmer diffusion in smectic liquid crystals

The dynamics of self-locomotion of active particles in aligned or liquid crystalline fluids strongly deviates from that in simple isotropic media. We explore the long-time dynamics of a swimmer moving in a three-dimensional smectic liquid crystal and find that the mean-square displacement (MSD) transverse to the director exhibits a distinct logarithmic tail at long times. The scaling is distinctly different from that in an isotropic or nematic fluid and hints at the subtle but important role of the director fluctuation spectrum in governing the long-time motility of active particles. Our findings are based on a generic hydrodynamic theory and Brownian dynamics computer simulation of a three-dimensional soft mesogen model.

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arXiv2018

Depletion-driven four-phase coexistences in discotic systems

Free volume theory (FVT) is a versatile and tractable framework to predict the phase behaviour of mixtures of platelets and non-adsorbing polymer chains in a common solvent. Within FVT, three principal reference phases for the hard platelets are considered: isotropic (I), nematic (N), and columnar (C). We derive analytical expressions that enable us to systematically trace the different types of phase coexistences revealed upon adding depletants and confirm the predictive power of FVT by testing the calculated diagrams against phase stability scenarios from computer simulation. A wide range of \textit{multi}-phase equilibria is revealed, involving two-phase isostructural transitions of all phase symmetries (INC) considered as well as the possible three-phase coexistences. Moreover, we identify the system parameters, relative disk shapes and colloid-polymer size ratios, at which four-phase equilibria are expected. These involve a remarkable coexistence of all three phase states commonly encountered in discotics including isostructural coexistences I$_1$-I$_2$-N-C, I-N$_1$-N$_2$-C, and I-N-C$_1$-C$_2$.

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arXiv2016

Simulating the pitch sensitivity of twisted nematics of patchy rods

Stiff, elongated biomolecules such as filamentous viruses, DNA or cellulose nanocrystals are known to form liquid crystals often exhibiting a helical supramolecular organization. Little is known about the microscopic origin, size and handedness of the helical pitch in these, so-called cholesteric phases. Experimental observations in chiral lyotropics suggest that long-ranged chiral forces of electrostatic origin acting between the mesogens are responsible for such organization. Using large-scale computer simulation we study the sensitivity of the pitch imparted by soft microscopic helices and confirm that the helical sense is sensitive to a change of packing fraction, magnitude of the molecular pitch and amplitude of the chiral interactions. In particular, we find evidence that the cholesteric helix sense may change spontaneously upon variation of particle density, at fixed molecular chirality. These pitch inversions have been reported in recent theoretical studies but simulation evidence remains elusive. We rationalize these sudden changes in the supramolecular helical symmetry on the basis of detailed measurements of the mean-torque generated by the twisting of the helices. The simulation methodology employed does not require confining the twisted nematic in a slab geometry and allows for a simultaneous measurement of the pitch and the twist elastic constant. We find that the twist elastic constant increases almost linearly with density suggesting that twisted nematic shows no signs of anomalous stiffening due to pre-smectic fluctuations at higher packing fraction.

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arXiv2016

Following fluctuating signs: anomalous active superdiffusion of swimmers in anisotropic media

Active (i.e., self-propelled or swimming) particles moving through an isotropic fluid exhibit conventional diffusive behavior. We report anomalous diffusion of an active particle moving in an anisotropic, nematic background. Whilst the translational motion parallel to the nematic director shows ballistic behavior, the long-time transverse motion is super-diffusive, with an anomalous scaling $\propto t \ln t$ of the mean squared displacement with time $t$. This behavior is predicted by an analytical theory that we present here, and is corroborated by numerical simulation of active particle diffusion in a simple lattice model for a nematic liquid crystal. It is universal for any collection of self-propelled elements (e.g., bacteria or active rods) moving in a nematic background, provided only that the swimmers are sufficiently dilute that their interactions with each other can be neglected, and that they do not perform "hairpin" turns.

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arXiv2013

Differently Shaped Hard Body Colloids in Confinement: From passive to active particles

We review recent progress in the theoretical description of anisotropic hard colloidal particles. The shapes considered range from rods and dumbbells to rounded cubes, polyhedra and to biaxial particles with arbitrary shape. Our focus is on both static and dynamical density functional theory and on computer simulations. We describe recent results for the structure, dynamics and phase behaviour in the bulk and in various confining geometries, e.g. established by two parallel walls which reduce the dimensionality of the system to two dimensions. We also include recent theoretical modelling for active particles, which are autonomously driven by some intrinsic motor, and highlight their fascinating nonequilibrium dynamics and collective behaviour.

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arXiv2013

Fluid dynamics of bacterial turbulence

Self-sustained turbulent structures have been observed in a wide range of living fluids, yet no quantitative theory exists to explain their properties. We report experiments on active turbulence in highly concentrated 3D suspensions of Bacillus subtilis and compare them with a minimal fourth-order vector-field theory for incompressible bacterial dynamics. Velocimetry of bacteria and surrounding fluid, determined by imaging cells and tracking colloidal tracers, yields consistent results for velocity statistics and correlations over two orders of magnitude in kinetic energy, revealing a decrease of fluid memory with increasing swimming activity and linear scaling between energy and enstrophy. The best-fit model parameters allow for quantitative agreement with experimental data.

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arXiv2012

Meso-scale turbulence in living fluids

Turbulence is ubiquitous, from oceanic currents to small-scale biological and quantum systems. Self-sustained turbulent motion in microbial suspensions presents an intriguing example of collective dynamical behavior amongst the simplest forms of life, and is important for fluid mixing and molecular transport on the microscale. The mathematical characterization of turbulence phenomena in active non-equilibrium fluids proves even more difficult than for conventional liquids or gases. It is not known which features of turbulent phases in living matter are universal or system-specific, or which generalizations of the Navier-Stokes equations are able to describe them adequately. Here, we combine experiments, particle simulations, and continuum theory to identify the statistical properties of self-sustained meso-scale turbulence in active systems. To study how dimensionality and boundary conditions affect collective bacterial dynamics, we measured energy spectra and structure functions in dense Bacillus subtilis suspensions in quasi-2D and 3D geometries. Our experimental results for the bacterial flow statistics agree well with predictions from a minimal model for self-propelled rods, suggesting that at high concentrations the collective motion of the bacteria is dominated by short-range interactions. To provide a basis for future theoretical studies, we propose a minimal continuum model for incompressible bacterial flow. A detailed numerical analysis of the 2D case shows that this theory can reproduce many of the experimentally observed features of self-sustained active turbulence.

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