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Grant J. Strachan

Publications and source records attributed to Grant J. Strachan.

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Competing ferroelectric and smectic order: modulated structures through molecular design

We demonstrate that the balance between polar and positional order can be systematically tuned through molecular engineering, providing direct control over the emergence of polar and modulated liquid-crystalline phases, allowing for versatile strategy for the design of functional ferroelectric soft materials. We show that polar orthogonal smectic phases (SmAF and SmAAF), promoted by the self-segregation of aromatic cores and sufficiently long terminal chains, are readily destabilized by strong longitudinal dipolar interactions that energetically penalize parallel alignment of molecular dipoles within a smectic layer. In contrast, the tilted ferroelectric SmCF phase is remarkably robust across the entire homologous series, indicating that molecular tilt efficiently relieves dipolar frustration within the smectic layers. We further demonstrate that the interplay between microsegregation and electrostatic interactions stabilizes the new modulated SmCM phase, characterized by incommensurate electron-density waves, particularly for compounds with short terminal chains. For longer homologs controlling the spatial distribution of fluorinated molecular fragments and terminal-chain length enabled the targeted formation of broken-layer-type modulated polar phases (2D or 3D).

cond-mat.soft

Competition between mirror symmetry breaking and translation symmetry breaking in ferroelectric liquid crystals with increasing lateral substitution

The recently discovered heliconical ferroelectric nematic (NTBF) phase is a unique example of spontaneous chiral symmetry breaking in a proper ferroelectric fluid. In this study, we investigate four homologous series of mesogenic compounds, differing in the degree of fluorination of the mesogenic core and bearing lateral alkoxy substituents of varying lengths, to understand how molecular architecture influences the formation and stability of the NTBF phase. Increasing the length of the lateral chain lowers the phase transition temperatures and suppresses smectic layer formation, enabling the emergence of the NTBF phase which replaces the orthogonal ferroelectric smectic A (SmAF) phase. This indicates a competition between lamellar and heliconical polar ordering, driven by the interplay of strong molecular dipoles and the self-segregation of chemically incompatible molecular segments that typically favor layered structures. Notably, the NTBF phase in these compounds exhibits exceptionally short helical pitch lengths, on the order of a few hundred nanometers, as revealed by selective light reflection and atomic force microscopy (AFM). Furthermore, for one of the studied compounds AFM imaging of one compound revealed a regular array of screw dislocations within the NTBF phase, suggesting a possible link to more complex modulated or twist-grain-boundary-like structures.

cond-mat.soft

Nematic and smectic phases with proper ferroelectric order

A material showing a sequence of three ferroelectric liquid crystalline phases below the paraelectric nematic phase has been synthesized and studied. The polar order of molecules appearing due to the dipole-dipole interactions in the NF phase is preserved also in the smectic phases: orthogonal SmAF and tilted SmCF. The ferroelectric ground state of both smectic phases is confirmed by their second harmonic generation activity and polarization switching. In the SmCF phase the polarization becomes oriented to the electric field by decreasing the tilt angle to zero. Although both smectic phases are ferroelectric in nature, their dielectric response is found to be very different.

cond-mat.soft

Temperature dependence of bend elastic constant in oblique helicoidal cholesterics

Elastic moduli of liquid crystals, known as Frank constants, are of quintessential importance for understanding fundamental properties of these materials and for the design of their applications. Although there are many methods to measure the Frank constants in the nematic phase, little is known about the elastic constants of the chiral version of the nematic, the so-called cholesteric liquid crystal, since the helicoidal structure of the cholesteric renders these methods inadequate. Here we present a technique to measure the bend modulus $K_{33}$ of cholesterics that is based on the electrically tunable reflection of light at an oblique helicoidal $Ch_{OH}$ cholesteric structure. $K_{33}$ is typically smaller than 0.6 pN, showing a non-monotonous temperature dependence with a slight increase near the transition to the twist-bend phase. $K_{33}$ depends strongly on the molecular composition. In particular, chiral mixtures that contain the flexible dimer 1'',7''-bis(4-cyanobiphenyl-4'-yl) heptane (CB7CB) and rod-like molecules such as pentylcyanobiphenyl (5CB) show a $K_{33}$ value that is 5 times smaller than $K_{33}$ of pure CB7CB or of mixtures of CB7CB with chiral dopants. Furthermore, $K_{33}$ in CB11CB doped with a chiral agent is noticeably smaller than $K_{33}$ in a similarly doped CB7CB which is explained by the longer flexible link in CB11CB. The proposed technique allows a direct in-situ determination of how the molecular composition, molecular structure and molecular chirality affect the elastic properties of chiral liquid crystals.

cond-mat.soft