Chiral heliconical ground state of nanoscale pitch in a nematic liquid crystal of achiral molecular dimers

Abstract

Freeze-fracture transmission electron microscopy study of the nanoscale structure of the so-called twist-bend" nematic phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reèeals stripe-textured fracture planes that indicate fluid layers periodically arrayed in the bulk with a spacing of d ∼ 8.3 nm. Fluidity and a rigorously maintained spacing result in long-range-ordered 3D focal conic domains. Absence of a lamellar X-ray reflection at waèeèector q ∼ 2π/d or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieèed with no detectable associatedmodulation of the electron density, and thus has nematic rather than smectic molecular ordering. A search for periodic ordering with d ∼ in CB(CH2)7CB using atomistic molecular dynamic computer simulation yields an equilibrium heliconical ground state, exhibiting nematic twist and bend, of the sort first proposed by Meyer, and enèisioned in systems of bent molecules by Dozoè and Memmer. We measure the director cone angle to be θTB ∼ 25° and the full pitch of the director helix to be pTB ∼ 8.3 nm, a èery small èalue indicating the strong coupling of molecular bend to director bend.