arXiv subjects

H. H. Wensink

Publications and source records attributed to H. H. Wensink.

At least 19 recordsLinked to original sources

arXiv2026

Shape enantiomerism in semi-rigid polymer liquid crystals

Weakly flexible, directed polymers can adopt a potentially infinite variety of conformations, some of them chiral. We develop a second-virial theory for semi-rigid polymers embedded in a nematic environment based on the assumption that the chains possess no intrinsic molecular chirality but can take on weakly helical conformations of either handedness. We demonstrate how these transient helical fluctuations can be exploited to predict the degree of chain stiffening induced by molecular crowding. The theoretical predictions are in good agreement with large-scale molecular dynamics simulations of bead-spring polymers with tunable backbone flexibility. Although both theory and simulations rule out spontaneous global chiral symmetry breaking imparted by chain conformations alone, they do reveal that polymers can develop pronounced enantiomeric shapes. Nematic fluids of semi-rigid polymers can be viewed as compensated cholesterics composed of transiently helical polymers with zero enantiomeric excess. By quantifying the degree of compensated chiral order developed over a broad range of concentrations and persistence lengths, two distinct regimes of weak and strong enantiomerism can be identified. A crossover between the two occurs when the chain persistence length drops below roughly three times the contour length.

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arXiv2023

Elastic response of colloidal smectics: insights from microscopic theory

Elongated colloidal rods at sufficient packing conditions are known to form stable lamellar or smectic phases. Using a simplified volume-exclusion model, we propose a generic equation-of-state for hard-rod smectics that is robust against simulation results and is independent of the rod aspect ratio. We then extend our theory by exploring the elastic properties of a hard-rod smectic, including the layer compressibility ($B$) and bending modulus ($K_{1}$). By introducing weak backbone flexibility we are able to compare our predictions with experimental results on smectics of filamentous virus rods and find quantitative agreement between the smectic layer spacing, the out-of-plane fluctuation strength, as well as the smectic penetration length $λ= \sqrt{K_{1}/B}$. We demonstrate that the layer bending modulus is dominated by director splay and depends sensitively on lamellar out-of-plane fluctuations that we account for on the single-rod level. We find that the ratio between the smectic penetration length and the lamellar spacing is about two orders of magnitude smaller than typical values reported for thermotropic smectics. We attribute this to the fact that colloidal smectics are considerably softer in terms of layer compression than their thermotropic counterparts while the cost of layer bending is of comparable magnitude.

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arXiv2021

Nemato-elasticity of hybrid molecular-colloidal liquid crystals

Colloidal rods immersed in a thermotropic liquid-crystalline solvent are at the basis of so-called hybrid liquid crystals which are characterized by tunable nematic fluidity with symmetries ranging from conventional uniaxial nematic or anti-nematic to orthorhombic [Mundoor et al., Science 360, 768 (2018)]. We provide a theoretical analysis of the elastic moduli of such systems by considering interactions between the individual rods with the embedding solvent through surface-anchoring forces, as well as steric and electrostatic interactions between the rods themselves. For uniaxial systems the presence of colloidal rods generates a marked increase of the splay elasticity which we found to be in quantitative agreement with experimental measurements. For orthorhombic hybrid liquid crystals we provide estimates of all twelve elastic moduli and show that only a small subset of those elastic constants play a relevant role in describing the nemato-elastic properties. The complexity and possibilities related to identifying the elastic moduli in experiments are briefly discussed. The results are expected to be helpful in stimulating future studies on defect-dressed "topological" colloids and the analysis of boundary-driven phenomena where the non-trivial director topology generated by biaxial nematics plays a key role.

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arXiv2020

Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures

Using a minimal algebraic model for the thermodynamics of binary rod--polymer mixtures, we provide evidence for a quintuple phase equilibrium; an observation that seems to be at odds with the Gibbs phase rule for two-component systems. Our model is based on equations of state for the relevant liquid crystal phases that are in quantitative agreement with computer simulations. We argue that the appearance of a quintuple equilibrium, involving an isotropic fluid, a nematic and smectic liquid crystal, and two solid phases can be reconciled with a generalized Gibbs phase rule in which the two intrinsic length scales of the athermal colloid--polymer mixture act as additional field variables.

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arXiv2020

Algebraic equations of state for the liquid crystalline phase behavior of hard rods

Based on simplifications of previous numerical calculations [Graf and Löwen, Phys. Rev. E \textbf{59}, 1932 (1999)], we propose algebraic free energy expressions for the smectic-A liquid crystal phase and the crystal phases of hard spherocylinders. Quantitative agreement with simulations is found for the resulting equations of state. The free energy expressions can be used to straightforwardly compute the full phase behavior for all aspect ratios and to provide a suitable benchmark for exploring how attractive interrod interactions mediate the phase stability through perturbation approaches such as free-volume or van der Waals theory.

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arXiv2019

Polymeric nematics of associating rods: phase behavior, chiral propagation and elasticity

Rod-shaped colloids with attractive tips can form linear aggregates that may subsequently undergo hierarchical self-assembly into nematic fluids. Inspired by recent modelling efforts on chromonic liquid crystals, composed of discotic building blocks, we formulate a second-virial theory for reversible supramolecular rods. Unlike chromonics, these systems are capable of forming stable nematic phases in the high-temperature, monomeric limit in the absence of polymerization. Changing the tip potential from attractive to repulsive thus enables a smooth crossover from a monomeric to a polymeric nematic fluid. We analyze the isotropic-nematic phase behavior for both regimes and address the nematic elastic properties. The theory accounts for the molecular flexibility and chirality of the filaments and respects the intrinsic chain-length dependence of nematic order. We also discuss the impact of polymerization inhibitors on the phase behavior in the polymeric regime and find that the inhibitors cause a marked narrowing of the isotropic-nematic biphasic region, and generate reentrance nematization as well as a mass density inversion of the coexisting phases. We finally discuss the elastic moduli of rod-based polymeric nematics by qualitative comparing their elastic anisotropies with those of chromonic liquid crystals and other nanoparticle-based nematics.

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arXiv2019

Effect of size polydispersity on the pitch of nanorod cholesterics

Many nanoparticle-based chiral liquid crystals are composed of polydisperse rod-shaped particles with considerable spread in size or shape, affecting the mesoscale chiral properties in, as yet, unknown ways. Using an algebraic interpretation of Onsager-Straley theory for twisted nematics, we investigate the role of length polydispersity on the pitch of nanorod-based cholesterics with a continuous length polydispersity, and find that polydispersity enhances the twist elastic modulus, $K_{2}$, of the cholesteric material without affecting the effective helical amplitude, $K_{t}$. In addition, for the infinitely large average aspect ratios considered here, the dependence of the pitch on the overall rod concentration is completely unaffected by polydispersity. For a given concentration, the increase in twist elastic modulus (and reduction of the helical twist) may be up to 50% for strong size polydispersity, irrespective of the shape of the unimodal length distribution. We also demonstrate that the twist reduction is reinforced in bimodal distributions, by doping a polydisperse cholesteric with very long rods. Finally, we identify a subtle, non-monotonic change of the pitch across the isotropic-cholesteric biphasic region.

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arXiv2018

Frank elasticity of composite colloidal nematics with anti-nematic order

Mixing colloid shapes with distinctly different anisotropy generates composite nematics in which the order of the individual components can be fundamentally different. In colloidal rod-disk mixtures or hybrid nematics composed of anisotropic colloids immersed in a thermotropic liquid crystal, one of the components may adopt so-called anti-nematic order while the other exhibits conventional nematic alignment. Focussing on simple models for hard rods and disks, we employ Onsager-Straley's second-virial theory to derive scaling expressions for the elastic moduli of rods and disks in both nematic and anti-nematic configurations and identify their explicit dependence on particle concentration and shape. We demonstrate that the splay, bend and twist elasticity of anti-nematically ordered particles scale logarithmically with the degree of anti-nematic order, with the bend-splay ratio for anti-nematic discotic nematics being far greater than for conventional nematic systems. The impact of surface anchoring on the elastic properties of hybrid nematics will also be discussed in detail. We further demonstrate that the elasticity of mixed uniaxial rod-disk nematics depends exquisitely on the shape of the components and we provide simple scaling expressions that could help engineer the elastic properties of composite nematic liquid crystals.

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arXiv2018

Elastic moduli of a smectic membrane: a rod-level scaling analysis

Chiral rodlike colloids exposed to strong depletion attraction may self-assemble into chiral membranes whose twisted director field differs from that of a 3D bulk chiral nematic. We formulate a simple microscopic variational theory to determine the elastic moduli of rods assembled into a bi-dimensional smectic membrane. The approach is based on a simple Onsager-Straley theory for a non-uniform director field that we apply to describe rod twist within the membrane. A microscopic approach enables a detailed estimate of the individual Frank elastic moduli (splay, twist and bend) as well as the twist penetration depth of the smectic membrane in relation to the rod density and shape. We find that the elastic moduli are distinctly different from those of a bulk nematic fluid, with the splay elasticity being much larger and the curvature elasticity much smaller than for rods assembled in a three-dimensional nematic fluid. We argue that the use of the simplistic one-constant approximation in which all moduli are assumed to be of equal magnitude is not appropriate for modelling the structure-property relation of smectic membranes.

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arXiv2017

Entropic patchiness drives multi-phase coexistence in discotic colloid-depletant mixtures

Entropy-driven equilibrium phase behaviour of hard particle dispersions can be understood from excluded volume arguments only. While monodisperse hard spheres only exhibit a fluid-solid phase transition, anisotropic hard particles such as rods, discs, cuboids or boards exhibit various multi-phase equilibria. Ordering of such anisotropic particles increases the free volume entropy by reducing the excluded volume between them. The addition of depletants gives rise to an entropic patchiness represented by orientation-dependent attraction resulting in non-trivial phase behaviour. We show that free volume theory is a simple, generic and tractable framework that enables to incorporate these effects and rationalise various experimental findings. Plate-shaped particles constitute the main building blocks of clays, asphaltenes and chromonic liquid crystals that find widespread use in the food, cosmetics and oil industry. We demonstrate that mixtures of platelets and ideal depletants exhibit a strikingly rich phase behaviour containing several types of three-phase coexistence areas and even a quadruple region with four coexisting phases.

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arXiv2017

Twisting with a twist: supramolecular helix fluctuations in chiral nematics

Most theoretical descriptions of lyotropic cholesteric liquid crystals to date focus on homogeneous systems in which the rod concentration, as opposed to the rod orientation, is uniform. In this work, we build upon the Onsager-Straley theory for twisted nematics and study the effect of weak concentration gradients, generated by some external potential, on the cholesteric twist. We apply our theory to chiral nematics of nanohelices in which the supramolecular helix sense is known to spontaneously change sign upon variation of particle concentration, passing through a so-called compensation point at which the mesoscopic twist vanishes. We show that the imposed field offers exquisite control of the handedness and magnitude of the helicoidal director field, even at weak field strengths. Within the same framework we also quantify the director fluctuation spectrum and find evidence for a correlation length diverging at the compensation point.

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arXiv2016

Empty smectics of hard nanorings: insights from a second-virial theory

Inspired by recent simulations on highly open liquid crystalline structures formed by rigid planar nanorings we present a simple theoretical framework explaining the prevalence of smectic over nematic ordering in systems of ring-shaped objects. The key part of our study is a calculation of the excluded volume of such non-convex particles in the limit of vanishing thickness to diameter ratio. Using a simple stability analysis we then show that dilute systems of ring-shaped particles have a strong propensity to order into smectic structures with an unusual antinematic order while solid disks of the same dimensions exhibit nematic order. Since our model rings have zero internal volume these smectic structures are essential empty, resembling the strongly porous structures found in simulation. We argue that the antinematic intralamellar order of the rings plays an essential role in stabilizing these novel smectic structures.

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arXiv2016

Spinodal instabilities in polydisperse lyotropic nematics

Many lyotropic liquid crystals are composed of mesogens that display a considerable spread in size or shape affecting their material properties and thermodynamics via various demixing and multi-phase coexistence scenarios. Starting from a generalized Onsager theory we formulate a generic framework that enables locating spinodal polydispersities as well as identifying the nature of incipient size fractionation for arbitrary model potentials and size distributions. We apply our theory to nematic phases of both hard rods and disks whose main particle dimension is described by a unimodal log-normal distribution. We find that both rod-based and discotic nematics become unstable at a critical polydispersity of about 20 %. We also investigate the effect of doping nematic assemblies with a small fraction of large species and highlight their effect on the stability of the uniform nematic fluid. We find that while rod-based are only weakly affected by the presence of large species, doping discotic nematics with very large platelets leads to a remarkable suppression of the spinodal instabilities. This could open up routes towards controlling the mechanical properties of nematic materials by manipulating the local stability of nematic fluid and its tendency to undergo fractionation-driven microphase separation.

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arXiv2015

Chiral assembly of weakly curled hard rods: effect of steric chirality and polarity

We theoretically investigate the pitch of lyotropic cholesteric phases composed of slender rods with steric chirality transmitted via a weak helical deformation of the backbone. In this limit, the model is amenable to analytical treatment within Onsager theory and a closed expression for the pitch versus concentration and helical shape can be derived. Within the same framework we also briefly review the possibility of alternative types of chiral order, such as twist-bend or screw-like nematic phases, finding that cholesteric order dominates for weakly helical distortions. While long-ranged or `soft' chiral forces usually lead to a pitch decreasing linearly with concentration, steric chirality leads to a much steeper decrease of quadratic nature. This reveals a subtle link between the range of chiral intermolecular interaction and the pitch sensitivity with concentration. A much richer dependence on the thermodynamic state is revealed for polar helices where parallel and anti-parallel pair alignments along the local director are no longer equivalent. It is found that weak temperature variations may lead to dramatic changes in the pitch, despite the lyotropic nature of the assembly.

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arXiv2015

Helical buckling in columnar assemblies of soft discotic mesogens

We investigate the emergence of chiral meso-structures in one-dimensional fluids consisting of stacked discotic particles and demonstrate that helical undulations are generated spontaneously from internal elastic stresses. The stability of these helical conformations arises from an interplay between long-ranged soft repulsions and nanopore confinement which is naturally present in columnar liquid crystals. Using a simple mean-field theory based on microscopic considerations we identify generic scaling expressions for the typical buckling radius and helical pitch as a function of the density and interaction potential of the constituent particles.

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arXiv2014

Spontaneous sense inversion in helical mesophases

We investigate the pitch sensitivity of cholesteric phases of helicoidal patchy cylinders as a generic model for chiral (bio-)polymers and helix-shaped colloidal rods. The behaviour of the macroscopic cholesteric pitch is studied from microscopic principles by invoking a simple density functional theory generalised to accommodate weakly twisted director fields. Upon changing the degree of alignment along the local helicoidal director we find that cholesteric phases exhibit a sudden sense inversion whereby the cholesteric phase changes from left- to right-handed and vice versa. Since the local alignment is governed by thermodynamic variables such as density, temperature or the amplitude of an external directional field such pitch sense inversions can be expected in systems of helical mesogens of both thermotropic and lyotropic origin. We show that the spontaneous change of helical symmetry is a direct consequence of an antagonistic effective torque between helical particles with a certain prescribed internal helicity. The results may help opening up new routes towards precise control of the helical handedness of chiral assemblies by a judicious choice of external control parameters.

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arXiv2013

Generalized Onsager theory for strongly anisometric patchy colloids

The implications of soft `patchy' interactions on the orientational disorder-order transition of strongly elongated colloidal rods and flat disks is studied within a simple Onsager-van der Waals density functional theory. The theory provides a generic framework for studying the liquid crystal phase behaviour of highly anisometric cylindrical colloids, which carry a distinct geometrical pattern of repulsive or attractive soft interactions localised on the particle surface. In this paper, we apply our theory to the case of charged rods and disks for which the local electrostatic interactions can be described by a screened-Coulomb potential. We consider infinitely thin rod-like cylinders with a uniform line charge and infinitely thin discotic cylinders with several distinctly different surface charge patterns. Irrespective of the backbone shape, the isotropic-nematic phase diagrams of charged colloids feature a generic destabilization of nematic order, a dramatic narrowing of the biphasic density region and a reentrant phenomenon upon reducing the electrostatic screening. At higher particle density the electrostatic repulsion leads to a complete suppression of nematic order in favour of spatially inhomogeneous liquid crystals.

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arXiv2013

Capturing self-propelled particles in a moving microwedge

Catching fish with a fishing net is typically done either by dragging a fishing net through quiescent water or by placing a stationary basket trap into a stream. We transfer these general concepts to micron-sized self-motile particles moving in a solvent at low Reynolds number and study their collective trapping behaviour by means of computer simulations of a two-dimensional system of self-propelled rods. A chevron-shaped obstacle is dragged through the active suspension with a constant speed $v$ and acts as a trapping "net". Three trapping states can be identified corresponding to no trapping, partial trapping and complete trapping and their relative stability is studied as a function of the apex angle of the wedge, the swimmer density and the drag speed $v$. When the net is dragged along the inner wedge, complete trapping is facilitated and a partially trapped state changes into a complete trapping state if the drag speed exceeds a certain value. Reversing the drag direction leads to a reentrant transition from no trapping, complete trapping, back to no trapping upon increasing the drag speed along the outer wedge contour. The transition to complete trapping is marked by a templated self-assembly of rods forming polar smectic structures anchored onto the inner contour of the wedge. Our predictions can be verified in experiments of artificial or microbial swimmers confined in microfluidic trapping devices.

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