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Chromonic liquid crystals are lyotropic nematic phases whose applications span from food to drug industries. It has recently been suggested that the elastic energy density governing the equilibrium distortions of these materials may be quartic in the measure of twist. Here we show that the non-linear twist-wave equation associated with such an energy has smooth solutions that break down in a finite time, giving rise to the formation of a shock wave, under rather generic assumptions on the initial profile. The critical time at which smooth solutions become singular is estimated analytically with an accuracy that numerical calculations for a number of exemplary cases prove to be satisfactory.

We study spontaneous deformations of a ribbon made of nematic polymer networks and activated under the action of a mechanical load. We show that when such ribbons are activated appropriately, the deformations produced can pull back and perform work against the externally applied load. We perform two numerical experiments to demonstrate this effect: (1) the \emph{pulling} experiment, where the ribbon is pulled longitudinally by a point force, and (2) the \emph{bending} experiment, where the ribbon is bent out of plane by a terminally applied point force. We quantify the capacity of the ribbon to work against external loads, and compute its dependence on both the ribbon thickness and the imprinted nematic texture (that is, the distribution of the nematic directors across the ribbon's length). Finally, we compute the efficiency of the activation process. Building on the outcomes of our numerical explorations, we formulate two educated conjectures on how the activation efficiency can in general be improved by acting on both the applied load and the imprinted nematic texture.

Minimal surfaces are ubiquitous in nature. Here they are considered as geometric objects that bear a deformation content. By refining the resolution of the surface deformation gradient afforded by the polar decomposition theorem, we identify a bending content and a class of deformations that leave it unchanged. These are the bending-neutral deformations, fully characterized by an integrability condition; they preserve normals. We prove that (1) every minimal surface is transformed into a minimal surface by a bending-neutral deformation, (2) given two minimal surfaces with the same system of normals, there is a bending-neutral deformation that maps one into the other, and (3) all minimal surfaces have indeed a universal bending content.

Twisted hedgehogs are defects in spherical cavities with homeotropic anchoring for the nematic director that arise when twist distortions are sufficiently less energetic than splay (and bend) distortions. They bear a characteristic inversion ring, where the director texture changes the sense it spirals about the center of the cavity. This paper applies a quartic twist theory recently proposed to describe the elasticity of chromonics to explain a series of inversion rings observed in aqueous solutions of SSY at two different concentrations. The theory features a phenomenological length a, whose measure is extracted from the data and shown to be fairly independent of the cavity radius, as expected for a material constant.

In this paper, we model the configurations of a system of hard rods by viewing each rod in a cell formed by its neighbors. By minimizing the free energy in the model and performing molecular dynamics, where, in both cases, the shape of the cell is a free parameter, we obtain the equilibrium orientational order parameter, free energy and pressure of the system. Our model enables the calculation of anisotropic stresses exerted on the walls of the cell due to shape change of the rod in photoisomerization. These results are a key step towards understanding molecular shape change effects in photomechanical systems under illumination., Comment: 15 pages, 8 figures

The elastic theory of chromonic liquid crystals is not completely established. We know, for example, that for anomalously low twist constants (needed for chromonics) the classical Oseen-Frank theory may entail paradoxical consequences when applied to describe the equilibrium shapes of droplets surrounded by an isotropic phase: contrary to experimental evidence, they are predicted to dissolve in a plethora of unstable smaller droplets. We proposed a quartic twist theory that prevents such an instability from happening. Here, we apply this theory to the data of two experiments devised to measure the planar anchoring strength at the plates bounding a twist cell filled with a chromonic liquid crystal; these data had before been interpreted within the Oseen-Frank theory. We show that the quartic twist theory affords a better agreement with the experimental data, while delivering in one case a larger value for the anchoring strength.

This paper, originally motivated by a question raised by Wood and Hanna [Soft Matter, 15, 2411 (2019)], shows that pure measures of bending for soft plates can be defined by introducing the class of bending-neutral deformations, finite incremental changes of the plate's shape bearing no further bending. This class of deformations is subject to a geometric compatibility condition, which is fully characterized. A tensorial pure measure of bending, which is accordingly invariant under bending-neutral deformations, is described in details. As shown by an illustrative class of examples, the general notion of pure measure of bending could be of use to formulate direct theories for soft plates, where stretching and bending energies are kept separate.

Chromonic nematics are lyotropic liquid crystals that have already been known for half a century, but have only recently raised interest for their potential applications in life sciences. Determining elastic constants and anchoring strengths for rigid substrates has thus become a priority in the characterization of these materials. Here, we present a method to determine chromonics' planar anchoring strength. We call it geometric as it is based on recognition and fitting of the stable equilibrium shapes of droplets surrounded by the isotropic phase in a thin cell with plates enforcing parallel alignments of the nematic director. We apply our method to shapes observed in experiments; they resemble elongated rods with round ends, which are called batonnets. Our theory also predicts other droplets' equilibrium shapes, which are either slender and round, called discoids, or slender and pointed, called tactoids. In particular, sufficiently small droplets are expected to display shape bistability, with two equilibrium shapes, one tactoid and one discoid, exchanging roles as stable and metastable shapes upon varying their common area.

In its most restrictive definition, an octupolar tensor is a fully symmetric traceless third-rank tensor in three space dimensions. So great a body of works have been devoted to this specific class of tensors and their physical applications that a review would perhaps be welcome by a number of students. Here, we endeavour to place octupolar tensors into a broader perspective, considering non-vanishing traces and non-fully symmetric tensors as well. A number of general concepts are recalled and applied to either octupolar and higher-rank tensors. As a tool to navigate the diversity of scenarios we envision, we introduce the octupolar potential, a scalar-valued function which can easily be given an instructive geometrical representation. Physical applications are plenty; those to liquid crystal science play a major role here, as they were the original motivation for our interest in the topic of this review.

Frustration in nematic-ordered media (endowed with a director field) is treated in a purely geometric fashion in a flat, two-dimensional space. We recall the definition of quasi-uniform distortions and envision these as viable ways to relieve director fields prescribed on either a straight line or the unit circle. We prove that using a planar spiral is the only way to fill the whole plane with a quasi-uniform distortion. Apart from that, all relieving quasi-uniform distortions can at most be defined in a half-plane; however, in a generic sense, they are all asymptotically spirals.

An elastic quartic twist theory has recently been proposed for chromonic liquid crystals, intended to overcome the paradoxical conclusions encountered by the classical Oseen-Frank theory when applied to droplets submerged in an isotropic fluid environment. However, available experimental data for chromonics confined to cylindrical cavities with degenerate planar anchoring on their lateral boundary can be explained equally well by both competing theories. This paper identifies a means to differentiate these theories both qualitatively and quantitatively. They are shown to predict quite different core defects for the twisted hedgehogs that chromonics generate when confined to a fixed spherical cavity with homeotropic anchoring. In the quartic twist theory, the defect core is estimated to be nearly one order of magnitude larger (tens of microns) than in the other and, correspondingly, the director field lines describe Archimedean spirals instead of logarithmic ones., Comment: arXiv admin note: text overlap with arXiv:2211.15820

Chromonic liquid crystals are lyotropic materials which are attracting growing interest for their adapatbility to living systems. To describe their elastic properties, the classical Oseen-Frank theory requires anomalously small twist constants and (comparatively) large saddle-splay constants, so large as to violate one of Ericksen's inequalities, which guarantee that the Oseen-Frank stored-energy density is bounded below. While such a violation does not prevent the existence and stability of equilibrium distortions in problems with fixed geometric confinement, the study of free-boundary problems for droplets has revealed a number of paradoxical consequences. Minimizing sequences driving the total energy to negative infinity have been constructed by employing ever growing needle-shaped tactoids incorporating a diverging twist [Phy. Rev. E 106, 044703 (2022)]. To overcome these difficulties, we propose here a novel elastic theory that extends for chromonics the classical Oseen-Frank stored energy by adding a quartic twist term. We show that the total energy of droplets is bounded below in the quartic twist theory, so that the known paradoxes are ruled out. The quartic term introduces a phenomenological length $a$ in the theory; this affects the equilibrium of chromonics confined within capillary tubes. Use of published experimental data allows us to estimate $a$.

We study the spontaneous out-of-plane bending of a planar untwisted ribbon composed of nematic polymer networks activated by a change in temperature. Our theory accounts for both stretching and bending energies, which compete to establish equilibrium. We show that when equilibrium is attained these energy components obey a \emph{complementarity} relation: one is maximum where the other is minimum. Moreover, we identify a \emph{bleaching} regime: for sufficiently large values of an activation parameter (which measures the mismatch between the degrees of order in polymer organization in the reference and current configurations), the ribbon's deformation is essentially independent of its thickness., Comment: Final published version

We study the equilibria of a photoresponsive nematic elastomer ribbon within a continuum theory that builds upon the statistical mechanics model put forward by Corbett and Warner [Phys. Rev. E 78, 061701 (2008)]. We prove that the spontaneous deformation induced by illumination is not monotonically dependent on the intensity $I$. The ribbon's deflection first increases with increasing $I$, as expected, but then decreases and abruptly ceases altogether at a critical value $I_\mathrm{e}$ of $I$. $I_\mathrm{e}$, which is enclosed within a hysteresis loop, marks a first-order shape transition. Finally, we find that there is a critical value of the ribbon's length, depending only on the degree of cross-linking in the material, below which no deflection can be induced in the ribbon, no matter how intense is the light shone on it.

Chromonic liquid crystals constitute a novel lyotropic phase, whose elastic properties have so far been modeled within the classical Oseen-Frank theory, provided that the twist constant is assumed to be considerably smaller than the saddle-splay constant, in violation of one Ericksen inequality. This paper shows that paradoxical consequences follow from such a violation for droplets of these materials surrounded by an isotropic fluid. For example, tactoids with a degenerate planar anchoring simply disintegrate indefinitely in myriads of smaller ones.

This paper proposes a theory that bridges classical analytical mechanics and nonequilibrium thermodynamics. Its intent is to derive the evolution equations of a system from a stationarity principle for a suitably augmented Lagrangian action. This aim is attained for homogeneous systems, described by a finite number of state variables depending on time only. In particular, it is shown that away from equilibrium free energy and entropy are independent constitutive functions.

The ground state of chromonic liquid crystals, as revealed by a number of recent experiments, is quite different from that of ordinary nematic liquid crystals: it is twisted instead of uniform. The common explanation provided for this state within the classical elastic theory of Frank demands that one Ericksen's inequality is violated. Since in general such a violation makes Frank's elastic free-energy functional unbounded below, the question arises as to whether the twisted ground state can be locally stable. We answer this question in the affirmative. In reaching this conclusion, a central role is played by the specific boundary conditions imposed in the experiments on the boundary of rigid containers and by a general formula that we derive here for the second variation of Frank's elastic free energy.

We present a theory of deformation of ribbons made of nematic polymer networks (NPNs). These materials exhibit properties of rubber and nematic liquid crystals, and can be activated by external stimuli of heat and light. A two-dimensional energy for a sheet of such a material has already been derived from the celebrated neo-classical energy of nematic elastomers in three space dimensions. Here, we use a dimension reduction method to obtain the appropriate energy for a ribbon from the aforementioned sheet energy. We also present an illustrative example of a rectangular NPN ribbon that undergoes in-plane serpentine deformations upon activation under an appropriate set of boundary conditions., Comment: Published version

Within this work we derive and analyse an expression for the free energy of a single-species system in the thermodynamic limit in terms of a generalised cavity volume, that is exact in general, and in principle applicable to systems across their entire range of density, as well as to particles within a general coordinate space. This provides a universal equation of state, and can thus relate the cavity volume to classical results, such as Mayer's cluster expansions. Through this we are able to provide some insight into the connections between cavity volume and free energy density, as well as their consequences. We use examples which permit explicit computations to further probe these results, reclaiming the exact results for a classical Tonks gas and providing a novel derivation of Onsager's free energy for a single species, isotropic system. Given the complexity of the problem we also provide a local lattice ansatz, exact in one dimension, with which we may approximate the cavity volume for hard sphere systems to provide an accurate equation of state in the cases of hard disks and spheres in both dilute regimes as well as beyond the freezing transition.

Self-action nonlinearity is a key aspect -- either as a foundational element or a detrimental factor -- of several optical spectroscopies and photonic devices. Supercontinuum generation, wavelength converters and chirped pulse amplification are just a few examples. The recent advent of Free Electron Lasers (FEL) fostered building on nonlinearity to propose new concepts and extend optical wavelengths paradigms for extreme ultraviolet (EUV) and X-ray regimes. No evidence for intrapulse dynamics, however, has been reported at such short wavelengths, where the light-matter interactions are ruled by the sharp absorption edges of core-electrons. Here, we provide experimental evidence for self-phase modulation of femtosecond FEL pulses, which we exploit for fine self-driven spectral tunability by interaction with sub-micrometric foils of selected monoatomic materials. Moving the pulse wavelength across the absorption edge, the spectral profile changes from a non-linear spectral blue-shift to a red-shifted broadening. These findings are rationalized accounting for ultrafast ionization and delayed thermal response of highly excited electrons above and below threshold, respectively., Comment: 20 pages, 6 figures

We study droplets of chromonic liquid crystals squeezed between parallel plates inducing degenerate tangential anchoring on the nematic director. In the coexistence regime, where droplets in the nematic phase are at equilibrium with the surrounding melt, our two-dimensional theoretical model predicts a regime of shape bistability for sufficiently large bipolar droplets, where tactoids (pointed shapes) and discoids (smooth shapes) coexist in equilibrium. This phenomenon has not yet been observed. Two-dimensional droplets of disodium cromoglycate (DSCG) have been the object of a thorough experimental study [Y.-K. Kim et al., J. Phys.: Condens. Matter 25, 404202 (2013)]. We show that our theory is in good quantitative agreement with these data and extract from them what promises to be a more accurate estimate for the isotropic surface tension at the nematic/melt interface of DSCG.

Nematic polymer networks (NPNs) are nematic elastomers within which the nematic director is enslaved to the elastic deformation. The elastic free energy of a NPN sheet of thickness $h$ has both stretching and bending components (the former scaling like h, the latter scaling like $h^3$). NPN sheets bear a director field $\mathbf{m}$ imprinted in them (usually, uniformly throughout their thickness); they can be activated by changing the nematic order (e.g. by illumination or heating). This paper illustrates an attempt to compute the bending energy of a NPN sheet and to show which role it can play in determining the activated shape. Our approach is approximate: the activated surface consists of flat sectors connected by ridges, where the unit normal jumps and the bending energy is concentrated. By increasing the number of ridges, we should get closer to the real situation, where the activated surface is smooth and the bending energy is distributed on it. The method is applied to a disk with imprinted a spiraling hedgehog. It is shown that upon activation the disk, like a tiny hand, is able to grab a rigid lamina.

Intense light-matter interactions and unique structural and electrical properties make Van der Waals heterostructures composed by Graphene (Gr) and monolayer transition metal dichalcogenides (TMD) promising building blocks for tunnelling transistors, flexible electronics, as well as optoelectronic devices, including photodetectors, photovoltaics and quantum light emitting devices (QLEDs), bright and narrow-line emitters using minimal amounts of active absorber material. The performance of such devices is critically ruled by interlayer interactions which are still poorly understood in many respects. Specifically, two classes of coupling mechanisms have been proposed: charge transfer (CT) and energy transfer (ET), but their relative efficiency and the underlying physics is an open question. Here, building on a time resolved Raman scattering experiment, we determine the electronic temperature profile of Gr in response to TMD photo-excitation, tracking the picosecond dynamics of the G and 2D bands. Compelling evidence for a dominant role ET process accomplished within a characteristic time of ~ 4 ps is provided. Our results suggest the existence of an intermediate process between the observed picosecond ET and the generation of a net charge underlying the slower electric signals detected in optoelectronic applications., Comment: 32 pages, 15 figures