arXiv subjects

Richard Mandle

Publications and source records attributed to Richard Mandle.

6 recordsLinked to original sources

arXiv2026

Molecular Hyperpolarisability as a Screening Descriptor for Second-Order Nonlinear Optics in Ferroelectric Nematic Liquid Crystals

Ferroelectric nematic liquid crystals combine fluidity with macroscopic polar order. Although the archetypal NF material RM734 exhibits large nonlinear optical coefficients, most known ferroelectric nematics were designed without consideration of optical nonlinearity. Here, we assess whether electronic-structure calculations can be used to identify promising nonlinear optical candidates within known polar liquid-crystal materials. Frequency-dependent molecular hyperpolarisability tensors were calculated using a range of DFT methods and basis sets, then converted to macroscopic d-coefficients using an oriented-gas model with empirical and values. Calculated values were benchmarked against available experimental d33, d15, and d13/d31 coefficients for representative materials. We find that absolute values depend strongly on method and bulk-parameter assumptions, whereas relative trends are more useful for screening. Explicit conformer averaging does not consistently improve agreement with experiment. Applying the best-performing single-conformer protocols to a broader polar liquid-crystal dataset identifies candidate materials with enhanced predicted nonlinear optical response and reveals simple design rules based on donor-acceptor asymmetry, conjugation length, and linker choice.

cond-mat.soft↗

arXiv2026

Exotic topological defects and director fields in free-floating spherical ferroelectric nematic liquid crystal shells

Ferroelectric nematic (NF) liquid crystals exhibit polar symmetry and large polarization, giving rise to phenomena absent in conventional apolar nematics. We investigate NF liquid crystals confined to free-floating spherical shells with tangential boundary conditions, enforcing a total topological defect charge of +2. We conjecture that ferroelectric nematics avoid splayed configurations with half-integer defects, common in apolar nematic shells, instead concentrating the topological charge into escaped azimuthal +1 defects requiring only bend and twist. Indeed, at room temperature in the NF phase, our thin RM734+DIO shells with inner and outer aqueous poly(vinyl alcohol) solutions develop an azimuthal director field around two antipodal +1 bend-twist defects. The non-centrosymmetric nature and the azimuthal director configuration of the shells in the NF phase are confirmed also through second-harmonic generation microscopy. At intermediate temperature the antiferroelectric Nx phase generates a new exotic texture rife in zigzag lines in the shells. In the regular N phase at high temperature, the shells develop the usual four +1/2 disclinations located near the thinnest point. Our study highlights the rich platform offered by spherical shells to study the behavior of exotic liquid crystals subject to topological constraints, possibly opening new paths to apply the highly responsive ferroelectric nematic phase

cond-mat.soft↗

arXiv2026

Polarization Plasticity of Ferroelectric Nematics: a case of Electrostatic Frustration in Simple Planar Electrode Cells

Because of their spontaneous bulk polarization, ferroelectric nematic liquid crystals can be easily brought by surface coupling or confinement in a state in which the accumulation of bound charges becomes incompatible with polar order, creating frustration. This condition also occurs in the simplest cells with parallel uncoated metal electrodes where we find that the polarization charge accumulating on the electrodes is proportional to the applied voltage for $\Delta V< V_{sat}$, a threshold value independent of cell thickness. We show that below $V_{sat}$, frustration drives the system into a regime of polarization plasticity, in which nematic ordering is preserved and the nematic director remains perpendicular to the electrodes, while instead the polarization is reduced to cancel the internal electric field. In this regime, the kinetics of bound charge reversal becomes independent from $\Delta V$. The observations are consistent with a model in which the system splits into antipolar tubular domains of mesoscale diameter extending from electrode to electrode, in which the polarization retains its unconstrained equilibrium value, separated by pure polarization-reversal walls.

cond-mat.soft↗

arXiv2025

Ultra-stretchable and Self-Healable Vitrimers with Tuneable Damping and Mechanical Response

Vitrimers are a relatively new class of polymer materials with unique properties offered by cross-links that can undergo associative exchange dynamics. We here present a new class of vitrimers based on poly(methyl acrylate) with cross-links utilising dioxaboralane metathesis. These vitrimers demonstrate a combination of ultra-stretchability (up to $\sim$ 80 times their own length), mechanical toughness ($\sim$ 40 MJ/m$^3$), and thermal stability up to $T\sim$ 250 {\deg}C; moreover, the vitrimers demonstrate excellent mechanical damping characterised by a loss factor ($\tan(\delta)$) with a maximum of $\sim$ 2-3 and an effective value $>$0.3 across five decades in frequency (0.001-100 Hz), or correspondingly across a $T$-range of $\sim$ 35 {\deg}C near room temperature (for a probe frequency of 1 Hz). The vitrimers can be successfully re-processed using both a thermo-mechanical and a chemical processing route, and can for low cross-link density self-heal at room temperature, making them suitable for sustainable applications. The material properties are directly tuneable by variation of both the amount of cross-linker and by the degree of curing. Thus, this class of vitrimers are promising for applications where stretchability combined with mechanical toughness and/or a high mechanical dissipation is required.

cond-mat.soft↗

arXiv2024

Spontaneous Symmetry Breaking in Polar Fluids

Spontaneous symmetry breaking and emergent polar order are each of fundamental importance to a range of scientific disciplines, as well as generating rich phase behaviour in liquid crystals (LCs). Here, we show the union of these phenomena to lead to two previously undiscovered polar liquid states of matter. Both phases have a lamellar structure with an inherent polar ordering of their constituent molecules. The first of these phases is characterised by polar order and a local tilted structure; the tilt direction precesses about a helix orthogonal to the layer normal, the period of which is such that we observe selective reflection of light. The second new phase type is anti-ferroelectric, with the constituent molecules aligning orthogonally to the layer normal. This has led us to term the phases the SmC_P^H and SmAAF phases, respectively. Further to this, we obtain room temperature ferroelectric nematic (NF) and SmC_P^Hphases via binary mixture formulation of the novel materials described here with a standard NF compound (DIO), with the resultant materials having melting points (and/or glass transitions) which are significantly below ambient temperature.

cond-mat.soft↗

arXiv2023

Room-temperature ferroelectric nematic liquid crystal showing a large and divergent density

The ferroelectric nematic phase (NF) is a recently discovered phase of matter in which the orientational order of the conventional nematic liquid crystal state is augmented with polar order. Atomistic simulations suggest that the polar NF phase would be denser than conventional nematics owing to contributions from polar order. Using an oscillating U-tube densitometer, we obtain detailed temperature-dependent density values for a selection of conventional liquid crystals with excellent agreement with earlier reports. Having demonstrated the validity of our method, we then record density as a function of temperature for M5, a novel room-temperature ferroelectric nematic material. We present the first experimental density data for a NF material as well as density data for a nematic that has not previously been reported. We find that the room-temperature NF material shows a large (>1.3 g cm3) density at all temperatures studied, with an increase in density at phase transitions. The magnitude of the increase for the intermediate splay-ferroelectric nematic (NX-NF) transition is an order of magnitude smaller than the isotropic-nematic (I-N) transition. Present results may be typical of ferroelectric nematic materials, potentially guiding material development, and is especially relevant for informing ongoing studies into this emerging class of materials.

cond-mat.soft↗