Induced Anticlinic Ordering and Nanophase Segregation of Bow-Shaped Molecules in a Smectic Solvent

Recent experiments indicate that doping low concentrations of bent-core molecules into calamitic smectic solvents can induce anticlinic and biaxial smectic phases. We have carried out Monte Carlo (MC) simulations of mixtures of rodlike molecules (hard spherocylinders with length/breadth ratio $L_{\rm rod}/D = 5$) and bow- or banana-shaped molecules (hard spherocylinder dimers with length/breadth ratio $L_{ban}/D = 5$ or 2.5 and opening angle $\psi$) to probe the molecular-scale organization and phase behavior of rod/banana mixtures. We find that a low concentration (3%) of $L_{ban}/D = 5$ dimers induces anticlinic (SmC$_A$) ordering in an untilted smectic (SmA) phase for $100^\circ \le \psi < 150^\circ$. For smaller $\psi$, half of each bow-shaped molecule is nanophase segregated between smectic layers, and the smectic layers are untilted. For $L_{ban}/D = 2.5$, no tilted phases are induced. However, with decreasing $\psi$ we observe a sharp transition from {\sl intralamellar} nanophase segregation (bow-shaped molecules segregated within smectic layers) to {\sl interlamellar} nanophase segregation (bow-shaped molecules concentrated between smectic layers) near $\psi = 130^\circ$. These results demonstrate that purely entropic effects can lead to surprisingly complex behavior in rod/banana mixtures.Comment: 5 pages Revtex, 7 postscript figure

Theory of Banana Liquid Crystal Phases and Phase Transitions

We study phases and phase transitions that can take place in the newly discovered banana (bow-shaped or bent-core) liquid crystal molecules. We show that to completely characterize phases exhibited by such bent-core molecules a third-rank tensor $T^{ijk}$ order parameter is necessary in addition to the vector and the nematic (second-rank) tensor order parameters. We present an exhaustive list of possible liquid phases, characterizing them by their space-symmetry group and order parameters, and catalog the universality classes of the corresponding phase transitions that we expect to take place in such bent-core molecular liquid crystals. In addition to the conventional liquid-crystal phases such as the nematic phase, we predict the existence of novel liquid phases, including the spontaneously chiral nematic $(N_T + 2)^*$ and chiral polar $(V_T + 2)^*$ phases, the orientationally-ordered but optically isotropic tetrahedratic $T$ phase, and a novel nematic $N_T$ phase with $D_{2d}$ symmetry that is neither uniaxial nor biaxial. Interestingly, the Isotropic-Tetrahedratic transition is {\em continuous} in mean-field theory, but is likely driven first-order by thermal fluctuations. We conclude with a discussion of smectic analogs of these phases and their experimental signatures.Comment: 28 pgs. RevTex, 32 eps figures, submitted to Phys. Rev.

Tilt order parameters, polarity and inversion phenomena in smectic liquid crystals

The order parameters for the phenomenological description of the smectic-{\it A} to smectic-{\it C} phase transition are formulated on the basis of molecular symmetry and structure. It is shown that, unless the long molecular axis is an axis of two-fold or higher rotational symmetry, the ordering of the molecules in the smectic-{\it C} phase gives rise to more than one tilt order parameter and to one or more polar order parameters. The latter describe the indigenous polarity of the smectic-{\it C} phase, which is not related to molecular chirality but underlies the appearance of spontaneous polarisation in chiral smectics. A phenomenological theory of the phase transition is formulated by means of a Landau expansion in two tilt order parameters (primary and secondary) and an indigenous polarity order parameter. The coupling among these order parameters determines the possibility of sign inversions in the temperature dependence of the spontaneous polarisation and of the helical pitch observed experimentally for some chiral smectic-{\it $C^{\ast}$} materials. The molecular interpretation of the inversion phenomena is examined in the light of the new formulation.Comment: 12 pages, 5 figures, RevTe

Phase Behavior of Bent-Core Molecules

Recently, a new class of smectic liquid crystal phases (SmCP phases) characterized by the spontaneous formation of macroscopic chiral domains from achiral bent-core molecules has been discovered. We have carried out Monte Carlo simulations of a minimal hard spherocylinder dimer model to investigate the role of excluded volume interations in determining the phase behavior of bent-core materials and to probe the molecular origins of polar and chiral symmetry breaking. We present the phase diagram as a function of pressure or density and dimer opening angle $\psi$. With decreasing $\psi$, a transition from a nonpolar to a polar smectic phase is observed near $\psi = 167^{\circ}$, and the nematic phase becomes thermodynamically unstable for $\psi < 135^{\circ}$. No chiral smectic or biaxial nematic phases were found.Comment: 4 pages Revtex, 3 eps figures (included

Poisson-bracket approach to the dynamics of bent-core molecules

We generalize our previous work on the phase stability and hydrodynamic of polar liquid crystals possessing local uniaxial $C_{\infty v}$-symmetry to biaxial systems exhibiting local $C_{2v}$-symmetry. Our work is motivated by the recently discovered examples of thermotropic biaxial nematic liquid crystals comprising bent-core mesogens, whose molecular structure is characterized by a non-polar body axis $({\bf{n}})$ as well as a polar axis $({\bf{p}})$ along the bisector of the bent mesogenic core which is coincident with a large, transverse dipole moment. The free energy for this system differs from that of biaxial nematic liquid crystals in that it contains terms violating the ${\bf{p}}\to -{\bf{p}}$ symmetry. We show that, in spite of a general splay instability associated with these parity-odd terms, a uniform polarized biaxial state can be stable in a range of parameters. We then derive the hydrodynamic equations of the system, via the Poisson-bracket formalism, in the polarized state and comment on the structure of the corresponding linear hydrodynamic modes. In our Poisson-bracket derivation, we also compute the flow-alignment parameters along the three symmetry axes in terms of microscopic parameters associated with the molecular geometry of the constituent biaxial mesogens.Comment: 16 pages, RevTeX, 1 figur