Proton and Deuterium NMR Study of the CBC9CB Dimer System.

Using proton and deuterium NMR spectroscopy, this work provides a description of the molecular orientational order of the mesogenic groups in both the Ntb and the classical nematic phase (N) of the liquid crystal dimer CB-C9-CB. The proton NMR data were collected at high field (7 T) with the nematic domains aligned by the field. Deuterium NMR data obtained from aligned samples at 11.7 T, published by Hoffmann , A. Soft Matter 2015 , 11 , 850 , were also considered in this study. Using the first-order perturbation theory, we carried out detailed simulations of the proton spectra from the terminal mesogenic groups along with the quadrupolar splittings from the carbon-deuterium bonds in the first chain positions, which allow for the determination of the Saupe order tensor for the mesogenic groups. We show that the main mechanism that induces the change of the 1H NMR spectrum and the quadrupolar splittings at the N-Ntb phase transition is the change of the orientation of the most ordered molecular frame (eigenframe of the Saupe tensor), along with the onset of the molecular biaxiality parameter, D. This orientation change is associated with the achiral symmetry breaking at the N-Ntb phase transition.

Mesophase structure and behaviour in bulk and restricted geometry of a dimeric compound exhibiting a nematic-nematic transition.

We present structural studies of a dimeric compound composed of a central heptyl spacer linking two mesogens consisting of terphenyl units at which two adjacent fluoro groups are attached to each central ring. The terminal rings are linked to pentyl chains as terminal groups. The material exhibits a nematic-nematic transition and a low temperature modulated phase. The higher temperature nematic phase was found to exhibit an anomaly of the bend elastic constant similar to that of the dimers with N-Ntb phase sequence, and the physical properties of the low-temperature nematic phase are similar to those of the known Ntb materials. The structure of the low-temperature modulated smectic/columnar phase is described together with its ability to form freely suspended films and fibres. The relation of the modulated structure to the fibre formation and to the appearance of the labyrinthine instability in freely-suspended films is discussed.

Anomalous Increase in Nematic-Isotropic Transition Temperature in Dimer Molecules Induced by a Magnetic Field.

We have determined the nematic-isotropic transition temperature as a function of an applied magnetic field in three different thermotropic liquid crystalline dimers. These molecules are comprised of two rigid calamitic moieties joined end to end by flexible spacers with odd numbers of methylene groups. They show an unprecedented magnetic field enhancement of nematic order in that the transition temperature is increased by up to 15 K when subjected to a 22 T magnetic field. The increase is conjectured to be caused by a magnetic-field-induced decrease of the average bend angle in the aliphatic spacers connecting the rigid mesogenic units of the dimers.

Second harmonic light scattering induced by defects in the twist-bend nematic phase of liquid crystal dimers.

The nematic twist-bend (NTB) phase, exhibited by certain thermotropic liquid crystalline (LC) dimers, represents a new orientationally ordered mesophase - the first distinct nematic variant discovered in many years. The NTB phase is distinguished by a heliconical winding of the average molecular long axis (director) with a remarkably short (nanoscale) pitch and, in systems of achiral dimers, with an equal probability to form right- and left-handed domains. The NTB structure thus provides another fascinating example of spontaneous chiral symmetry breaking in nature. The order parameter driving the formation of the heliconical state has been theoretically conjectured to be a polarization field, deriving from the bent conformation of the dimers, that rotates helically with the same nanoscale pitch as the director field. It therefore presents a significant challenge for experimental detection. Here we report a second harmonic light scattering (SHLS) study on two achiral, NTB-forming LCs, which is sensitive to the polarization field due to micron-scale distortion of the helical structure associated with naturally-occurring textural defects. These defects are parabolic focal conics of smectic-like "pseudo-layers", defined by planes of equivalent phase in a coarse-grained description of the NTB state. Our SHLS data are explained by a coarse-grained free energy density that combines a Landau-deGennes expansion of the polarization field, the elastic energy of a nematic, and a linear coupling between the two.

Similarities and differences between molecular order in the nematic and twist-bend nematic phases of a symmetric liquid crystal dimer.

The order parameter, Szz, where z is the para axis of the difluoroterphenyl groups in DTC5C9, has been obtained from chemical shift anisotropies measured by (13)C - {(1)H} NMR experiments at temperatures throughout the nematic, NU, and twist-bend nematic, NTB, phases shown by this compound. The order parameter temperature profiles are unusual in having a maximum value in the NU phase and then decreasing until the NTB phase is reached. There is a small discontinuity (∼2%) in Szz at TNNTB and then a gradual decrease until a new phase appears. This behaviour is interpreted as revealing a temperature-dependent tilting of local directors in both phases away from the applied magnetic field direction. In the enantiomorphic twist-bend phase this tilt is consistent with the structure of the phase as a helical arrangement of local directors, whilst in the high-temperature non-chiral nematic the tilt must involve a non-chiral arrangement. It is proposed that in both phases the tilting of directors has a common origin in the bent shape of the molecules.

Nematic twist-bend phase with nanoscale modulation of molecular orientation.

A state of matter in which molecules show a long-range orientational order and no positional order is called a nematic liquid crystal. The best known and most widely used (for example, in modern displays) is the uniaxial nematic, with the rod-like molecules aligned along a single axis, called the director. When the molecules are chiral, the director twists in space, drawing a right-angle helicoid and remaining perpendicular to the helix axis; the structure is called a chiral nematic. Here using transmission electron and optical microscopy, we experimentally demonstrate a new nematic order, formed by achiral molecules, in which the director follows an oblique helicoid, maintaining a constant oblique angle with the helix axis and experiencing twist and bend. The oblique helicoids have a nanoscale pitch. The new twist-bend nematic represents a structural link between the uniaxial nematic (no tilt) and a chiral nematic (helicoids with right-angle tilt).

Spontaneous periodic deformations in nonchiral planar-aligned bimesogens with a nematic-nematic transition and a negative elastic constant.

Hydrocarbon linked mesogenic dimers are found to exhibit an additional nematic phase below the conventional uniaxial nematic phase as confirmed by x-ray diffraction. The phase produces unusual periodic stripe domains in planar cells. The stripes are found to be parallel to the rubbing direction (in rubbed cells) with a well-defined period equal to double the cell gap. The stripes appear without external electromagnetic field, temperature or thickness gradients, rubbing or hybrid alignment treatments. Simple modeling proposes a negative sign for at least one of the two elastic constants: splay and twist, as a necessary condition for the observed pattern.

Electro-optic characterization of a nematic phase formed by bent core mesogens.

The purpose of this paper is the demonstration that bent core nematic phases behave quantitatively and qualitatively very different from ordinary calamitic nematics in their electro-optical characteristics. We present measurements of the elastic properties from the analysis of Brochard-Leger walls that are formed during the splay Fréedericksz transition in sandwich cells. These walls possess an unusually large shape anisotropy as compared to similar structures in calamitic nematics. The wall shapes can be explained when one assumes that the bend elastic constant K(33) is one order of magnitude larger than the twist constant K(22) of the material, supposing that flexoelectricity in the description of the elastic deformations can be neglected. Further we report periodic structures above the splay Fréedericksz transition with a wave vector perpendicular to the director easy axis. They represent either a static instability or an unconventional type of electrically driven convection.

Field-induced texture transitions in a bent-core nematic liquid crystal.

It is demonstrated in electro-optic experiments that an external electric field of the order of 10;{5} V/m induces persisting texture transitions in a nematic phase formed by bent-core mesogens. The field-induced metastable state is identified by its optical and electric properties. After the field is switched off, the original and induced states can coexist in domains for about one hour in planar sandwich cells. During this time, the induced domains gradually shrink but they can be stabilized in moderate electric fields. The occurrence of similar domains in homeotropic cells suggests that the transition into a metastable biaxial state is observed. In the field-free planar ground state, the formation of inversion walls is observed inside the metastable domains.

Determination of lead in stainless steel by atomic-absorption spectroscopy.

A method has been developed for the determination of lead in stainless steels by atomic-absorption spectrometry after removal of iron by solvent extraction and volatilization of chromium as chromyl chloride. The method proposed is suitable for the determination of lead in the range from 5 to 100 ppm.