Interlayer structures of the chiral smectic liquid crystal phases revealed by resonant X-ray scattering.

The structures of the liquid crystalline chiral subphases exhibited by several materials containing either a selenium or sulphur atom have been investigated using a resonant x-ray scattering technique. This technique provides a unique structural probe for the ferroelectric, ferrielectric, antiferroelectric, and SmC(*)(alpha) phases. An analysis of the scattering features allows the structural models of the different subphases to be distinguished, in addition to providing a measurement of the helical pitch. This paper reports resonant scattering features in the antiferroelectric hexatic phase, the three- and four-layer intermediate phases, the antiferroelectric and ferroelectric phases and the SmC(*)(alpha) phase. The helicoidal pitch has been measured from the scattering peaks in the four-layer intermediate phase as well as in the antiferroelectric and ferroelectric phases. In the SmC(*)(alpha) phase, an investigation into the helical structure has revealed a pitch ranging from 5 to 54 layers in different materials. Further, a strong resonant scattering signal has been observed in mixtures of a selenium containing material with as much as 90% nonresonant material.

Orientational ordering in the chiral smectic-C*FI2 liquid crystal phase determined by resonant polarized x-ray diffraction.

High-resolution resonant polarized x-ray diffraction experiments near the sulfur K edge have been performed on free-standing liquid crystal films exhibiting the chiral smectic-C*FI2 phase. It is widely accepted that this phase has a four-layer repeat unit, but the internal structure of the repeat unit remains controversial. We report different resolved features of the resonant x-ray diffraction peaks associated with the smectic-C*FI2 phase that unambiguously demonstrate that the four-layer repeat unit is locally biaxial about the layer normal and that the measured angle, describing the biaxiality, is in good agreement with optical measurements.

Resonant x-ray scattering study of the antiferroelectric and ferrielectric phases in liquid crystal devices.

Resonant x-ray scattering has been used to investigate the interlayer ordering of the antiferroelectric and ferrielectric smectic C* subphases in a device geometry. The liquid crystalline materials studied contain a selenium atom and the experiments were carried out at the selenium K edge allowing x-ray transmission through glass. The resonant scattering peaks associated with the antiferroelectric phase were observed in two devices containing different materials. It was observed that the electric-field-induced antiferroelectric to ferroelectric transition coincides with the chevron to bookshelf transition in one of the devices. Observation of the splitting of the antiferroelectric resonant peaks as a function of applied field also confirmed that no helical unwinding occurs at fields lower than the chevron to bookshelf threshold. Resonant features associated with the four-layer ferrielectric liquid crystal phase were observed in a device geometry. Monitoring the electric field dependence of these ferrielectric resonant peaks showed that the chevron to bookshelf transition occurs at a lower applied field than the ferrielectric to ferroelectric switching transition.

Phase transition between single crystals of two thermotropic cubic phases from a mixture of 3,5-didodecyloxybenzoic acid and C18-ANBC.

A reversible phase transition between two different thermotropic cubic phases is observed in a mixture of two carboxylic acids. Such a transition was characterised by single-crystal X-ray diffraction and direct optical microscopy; an image of a facetted droplet just at the transition between the two phases is shown in the picture.

Structures of chiral smectic-C mesophases revealed by polarization-analyzed resonant x-ray scattering.

We report polarization-analyzed, resonant x-ray diffraction at the sulfur K edge performed upon free-standing liquid-crystal films. Our studies of the thiobenzoate liquid-crystal enantiomer 10OTBBB1M7 yield the polarization states of resonant satellite peaks arising from characteristic superlattices in the chiral smectic-C (SmC(*)) variant phases, including the antiferroelectric SmC(*)(A), ferrielectric SmC(*)(FI1) and SmC(*)(FI2), as well as SmC(*)(alpha). The observed polarizations agree with the clock model of chiral smectic-C variants, and rule out other proposals made to date for these structures. Data from the 10OTBBB1M7 racemate also support the clock model. Our resonant diffraction results from a thiophene liquid-crystal compound reveal the same superlattice periodicities seen in corresponding antiferroelectric and ferrielectric phases of 10OTBBB1M7.

Tensorial x-ray structure factor in smectic liquid crystals.

The amplitudes and the polarizations of the different resonant reflections characterizing the modulation of the orientational order in smectic liquid crystals are derived from the molecular tensorial structure factor. In the case of a commensurate helicoidal modulation, our conclusions are consistent with the previous predictions of Dimitrienko. We have extended Dimitrienko's prediction to incommensurate helicoidal structures and to commensurate but nonhelicoidal modulations. We have compared the estimated values for different models of modulations with the same period, with the experimental data obtained on different smectic-C variants. These comparisons enable us to discriminate between the different models.

The highly concentrated liquid-crystalline phase of DNA is columnar hexagonal.

The DNA molecule is extremely compacted in bacteria, in cell nuclei, sperm heads and virus capsids. These interactions between DNA molecules are important to our understanding of chromatin condensation. DNA forms multiple liquid-crystalline phases whose nature depends on the polymer concentration, and it has been suggested that the highly concentrated phase of 50-nm DNA molecules is two-dimensionally ordered and smectic-like. We rule out this smectic hypothesis and demonstrate by polarizing microscopy, electron microscopy and X-ray diffraction that this phase is characterized by a columnar longitudinal order and a hexagonal lateral order, with intermolecular distances ranging from 2.8 to 4.0 nm depending on the DNA concentration.