The liquid-crystal dimer 1'',7''-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB) exhibits two liquid-crystalline mesophases on cooling from the isotropic phase. The high-temperature phase is nematic; the identification and characterization of the other liquid-crystal phase is reported in this paper. It is concluded that the low-temperature mesophase of CB7CB is a new type of uniaxial nematic phase having a nonuniform director distribution composed of twist-bend deformations. The techniques of small-angle x-ray scattering, modulated differential scanning calorimetry, and dielectric spectroscopy have been applied to establish the nature of the nematic-nematic phase transition and the structural features of the twist-bend nematic phase. In addition, magnetic resonance studies (electron-spin resonance and (2)H nuclear magnetic resonance) have been used to investigate the orientational order and director distribution in the liquid-crystalline phases of CB7CB. The synthesis of a specifically deuterated sample of CB7CB is reported, and measurements showed a bifurcation of the quadrupolar splitting on entering the low-temperature mesophase from the high-temperature nematic phase. This splitting could be interpreted in terms of the chirality of the twist-bend structure of the director. Calculations using an atomistic model and the surface interaction potential with Monte Carlo sampling have been carried out to determine the conformational distribution and predict dielectric and elastic properties in the nematic phase. The former are in agreement with experimental measurements, while the latter are consistent with the formation of a twist-bend nematic phase.
One of the defining characteristics of the twist-bend nematic phase, formed by the methylene-linked liquid crystal dimer 1″,7″-bis(4-cyanobiphenyl-4'-yl) heptane (CB7CB), is its chirality. This new nematic phase, predicted by Dozov, is of particular interest because although the constituent molecules are achiral the phase itself is chiral. Here, we describe the use of NMR spectroscopy to determine experimentally whether in reality the phase is chiral or not. The basis of this novel procedure is that the equivalence of the protons or deuterons in a prochiral methylene group in a nematic phase with D∞h symmetry is lost in a chiral phase because its symmetry is reduced to D∞ on removal of the mirror plane. Recording proton-enhanced local field (PELF) NMR experiments shows that in the standard nematic phase all of the methylene groups in the heptane spacer have equivalent pairs of C-H groups but this equivalence is lost for the six prochiral methylene groups with their enantiotopic protons on passing to the twist-bend nematic. Strikingly, this equivalence is not lost for the central methylene group where the two protons are homotopic. We also show how the phase chirality can be demonstrated with probe molecules which contain deuteriated prochiral methylene groups, using 4-octyl-4'-cyanobiphenyl-d2, perdeuteroacenaphthene-d10, and acenaphthene-d4 as examples. For the standard nematic phase deuterium, NMR shows that the deuterons in these methylene groups are equivalent but, as expected, in the twist-bend nematic phase this equivalence is lost. The deuterium NMR spectra of these probe molecules dissolved in CB7CB have been recorded from the isotropic phase, through the nematic and deep into the supercooled twist-bend nematic.
Here we report the chemical induction of the twist-bend nematic phase in a nematic mixture of ether-linked liquid crystal dimers by the addition of a dimer with methylene links; all dimers have an odd number of groups in the spacer connecting the two mesogenic groups. The twist-bend phase has been identified from its optical texture and x-ray scattering pattern as well as NMR spectroscopy, which demonstrates the phase chirality. Theory predicts that the key macroscopic property required for the stability of this chiral phase formed from achiral molecules is for the bend elastic constant to tend to be negative; in addition the twist elastic constant should be smaller than half the splay elastic constant. To test these important aspects of the prediction we have measured the bend and splay elastic constants in the nematic phase preceding the twist-bend nematic using the classic Frederiks methodology and all three elastic constants employing the dynamic light scattering approach. Our results show that, unlike the splay, the bend elastic constant is small and decreases significantly as the transition to the induced twist-bend nematic phase is approached, but then exhibits unexpected behavior prior to the phase transition.
We extend the twist-bend nematic (N(TB)) model to describe the electro-optics of this novel phase. We predict an electroclinic effect (ECE) subject to a dc electric field E applied perpendicular to the helix axis or wave vector q, with rotation of the N(TB) optic axis around E. This linear effect, with its flexoelectric origin, is a close analog to the electro-optic effects observed for chiral liquid crystals. However, in nematics composed of achiral molecules having a bent shape, it is the electro-optic signature of the N(TB) phase. We test our model experimentally in the low-temperature nematic phase of the odd liquid crystal dimer, CB7CB, with its molecules having, on average, a bent shape. The ECE measurements confirm the previously proposed twist-bend nematic structure of this phase, with its broken chiral symmetry, extremely short (<10 nm) doubly degenerate pitch and ultrafast, submicrosecond response times.
The Gay–Berne potential is proving to be a valuable model with which to investigate the behavior of liquid crystals using computer simulation techniques. The potential contains four independent parameters which control the anisotropy in the attractive and repulsive interactions. The choice of these parameters is not straightforward and it would seem that those employed in some simulations are not strictly appropriate for mesogenic rodlike molecules. Here we report a detailed computer simulation study of Gay–Berne particles interacting via a potential parametrized to reflect the anisotropic forces based on a fit to a realistic mesogenic molecule. The behavior of the phases and the transitions between them have been investigated for a system of 2000 particles using isothermal–isobaric Monte Carlo simulations. At low pressures, this Gay–Berne mesogen exhibits isotropic, smectic A and smectic B phases but, as the pressure is increased, so a nematic phase is added to the sequence. The nature of the phase transitions and the phase diagram are compared where possible with those of real mesogens. The structures of the four phases have been investigated in detail for a larger system of 16 000 particles using canonical molecular dynamics simulations at state points taken from the phase diagram determined from the Monte Carlo simulations. A wide range of singlet and pair distribution functions were evaluated together with orientational correlation coefficients and, for the smectic phases, a bond orientation correlation function. The results for these properties were used to identify the phases, to consider their structure at a quantitative level and, where possible, to make contact with experimental studies and the predictions of theories of liquid crystals. It would appear that with this parametrization, the Gay–Berne potential provides a powerful tool with which to understand the behavior of real liquid crystals and to test the predictions of theory.
Precise birefringence measurements in large monodomains of the twist-bend nematic phase strongly support its heliconical structure and doubly degenerate handedness.
Most molecular theories of nematic liquid crystals assume that the constituent molecules are cylindrically symmetric. However, although this may be a useful approximation the molecules of real nematogens are of lower symmetry ; here we develop a theory for an ensemble of such particles based on a general expansion of the pairwise intermolecular potential together with the molecular field approximation. The dependence of the orientational properties of the uniaxial mesophase on the deviation from molecular cylindrical symmetry is calculated from the series expansio n of the pseudopotential. In these calculations the number of arbitrary parameters in the orientational pseudo-potential is reduced by assuming that the anisotropic intermolecular potential originates solely from dispersion forces. The theoretical predictions for the values of the ordering matrix and the entropy change at the nematic-isotropic transition are found to be in good agreement with those observed for 4,4'-dimethoxyazoxybenzene. In addition, the theory provides a reasonable account of the temperature dependence of the order parameter at constant volume for this nematogen. The allowance for deviations from molecular cylindrical symmetry appears to remove many of the discrepancies between the Maier-Saupe theory and experiment.
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