Raman scattering studies of order parameters in liquid crystalline dimers exhibiting the nematic and twist-bend nematic phases

Polarized Raman Spectroscopy (PRS) is used to quantify the orientational order in the conventional (N) and twist-bend (NTB) nematic phases of a homologous series of liquid crystalline dimers. The dimers investigated have 7, 8, 9 and 11 methylene groups connecting two cyanobiphenyl mesogens and data for 4-pentyl-4'-cyanobiphenyl (5CB) and 4-octyl-4'-cyanobiphenyl (8CB) are included for comparison. Simulated and measured Raman spectra for the materials are compared. PRS is used to determine both (P2) and (P4) order parameters across the nematic temperature range and immediately below the NTB–N phase transition using a model that takes into account the molecular bend of the odd dimers, which is described in detail. In the nematic phase, the odd dimers are found to exhibit rather low order parameters with hP2i taking values between 0.3 and 0.5 and (P4) about 0.25. In contrast, the even dimer shows extremely high values of the order parameters with (P2) taking values between 0.7 and 0.8 and (P4) between 0.4 and 0.45. For the odd dimers, the values of (P2) in the NTB phase are similar to those of the N phase, whereas (P4) jumps by approximately 5–10% and then decreases with temperature. On comparing the experimental data with the theoretical predictions, we find reasonable qualitative agreement for all materials with molecular field theory. The odd dimers, however, show higher (P4) values than obtained from theoretical models, a factor attributed to the neglect of molecular flexibility and biaxiality in the PRS analysis

The Dependency of Nematic and Twist-bend Mesophase Formation on Bend Angle

We have prepared and studied a family of cyanobiphenyl dimers with varying linking groups with a view to exploring how molecular structure dictates the stability of the nematic and twist-bend nematic mesophases. Using molecular modelling and 1D (1)H NOESY NMR spectroscopy, we determine the angle between the two aromatic core units for each dimer and find a strong dependency of the stability of both the nematic and twist-bend mesophases upon this angle, thereby satisfying earlier theoretical models

Conformational landscapes of bimesogenic compounds and their implications for the formation of modulated nematic phases

The twist-bend phase (NTB) is most commonly observed in materials with a gross-bent shape: dimers; bent-cores; bent-oligomers. We had suggested previously that the bend-angle of such systems effectively dictates the relative thermal stability of the NTB phase. However, our earlier paper relied on the use of a single energy-minimum conformer and so failed to capture any information about flexibility and conformational distribution. In the present work, we revisit our hypothesis and examine a second set of dimers with varying linking groups and spacer composition. We have improved on our earlier work by studying the conformational landscape of each material, allowing average bend-angles to be determined as well as the conformer distribution. We observe that the stability of the NTB phase exhibits a strong dependence not only on the Boltzmann-weighted average bend-angle (rather than just a static conformer), but also on the distribution of conformers. To a lesser extent, the flexibility of the spacer appears important. Ultimately, this work satisfies both theoretical treatments and our initial experimental study and demonstrates the importance of molecular bend to the NTB phase

Combined Microscopy, Calorimetry and X-ray Scattering Study of Fluorinated Dimesogens

The material FDO11DFCB3 (compound 2 in this work) remains the only example of a liquid-crystalline material to exhibit a phase transition from the heliconical twist-bend phase into a lamellar smectic A mesophase, additionally this material exhibits a previously unidentified mesophase. We have prepared and characterised several homologues of this compound, with each material subjected to an in-depth analysis by optical microscopy, calorimetry and small angle X-ray scattering studies. Despite FDO11DFCB3 being similar in chemical structure to the novel materials presented herein its liquid-crystalline behaviour is rather different, indicating an unexpected sensitivity of the twist-bend phase to molecular structure

Low-temperature scanning tunneling microscope for investigations in magnetic fields

A scanning tunneling microscope (STM), equipped with an attachment for in situ sample cleavage and capable of low-temperature measurements in the presence of a strong magnetic field, is described, Details of the constructions of the cryostat insert, mechanical head, and cleavage mechanism are described. Performance of the STM is demonstrated by the results of investigation of the single-crystal surface of InAs, Ga, and high-temperature superconductor BiSiCaCuO ceramics. The tunneling gap in the magnetic field is about 15 nm/T, and the transverse STM probe point shift, about 3 nm/T