Comparison between experiment and theory in the temperature variation of film tension above the bulk isotropic transition in free-standing liquid-crystal films.

Using differential scanning calorimetry, the transition enthalpies and temperatures for the bulk smectic-isotropic phase transition have been measured for a series of liquid-crystal compounds. For five compounds, those values were used as parameters in a microscopic mean-field model to predict the temperature dependence of the difference in free-energy density between a sample of material in a free-standing smectic film and that in the bulk. The model predicts a weak temperature dependence below the bulk clearing point and a pronounced monotonic increase with temperature above the transition temperature. The compounds used in this study were chosen specifically because they were also the subject of a previous independent experimental study [M. Veum, Phys. Rev. E 74, 011703 (2006)] that demonstrated a sudden monotonic increase in the free-standing film tension with temperature, which is qualitatively consistent with the predictions of the above-mentioned mean-field model. This study presents a direct and quantitative comparison between the predictions of the mean-field model and the results from previous tension experiments.

Role of molecular weight and phase sequence in the temperature variation of film tension above the bulk isotropic transition in freestanding liquid-crystal films.

Building upon our previous report [Veum, Phys. Rev. E 17, 020701(R) (2005)] involving two compounds, we have performed a systematic study of the temperature variation of film tension above the bulk isotropic transition in freestanding films to include a total of six smectic liquid-crystal compounds. Consistent with the previous results, the tension increases sharply with temperature above the transition, the tension-temperature slope is proportional to the film's thickness, and the data can be interpreted in the context of theoretical models for layer thinning. Our data suggest that both molecular weight and bulk phase appearing below its isotropic phase play important roles in the slope values.

Temperature variation of film tension above the bulk smectic-A-isotropic transition in freestanding liquid-crystal films.

We have measured the temperature variation of film tension above the bulk smectic-A-isotropic transition in freestanding films of two liquid-crystal compounds. Above the transition, the tension increases sharply with temperature, and the slope is proportional to the film's thickness regardless of whether or not the compound exhibits regular layer-by-layer thinning. The data can be interpreted in the context of theoretical models for layer thinning.

Unusual thickness-dependent heat-capacity anomalies in free-standing hexatic liquid-crystal films.

High-resolution heat-capacity and optical-reflectivity measurements have been conducted near the smectic-A to hexatic-B transition in thin free-standing films of the liquid-crystal compound 64COOBC. We find an unexpected dependence on film thickness of the integrated magnitude of the heat-capacity anomalies as the films undergo layer-by-layer transitions. We measure the penetration depths of the ordering from the surface and next-to-surface layers which are pertinent to the highly correlated thermal behavior.

How do smectic liquid crystals of different molecular length mix in thin films?

We present a model for the structure of binary mixtures of smectic compounds in freely suspended films of 2-7 layers. The compounds are the hexyl (6AB) and dodecyl (10AB) homologues of p, p'-dialkylazoxybenzene that differ by about 40% in molecular length. X-ray reflectivity indicates that no demixing occurs between 6AB and 10AB molecules, while also there is no indication found of increased roughness at the film surfaces. However, the surface layers are somewhat expanded compared to the interior layers. This can be explained by backfolding of the dodecyl end chains of 10AB molecules at the surface via two gauche kinks, which ensures dense packing. This model is supported by surface tension measurements that indicate an increased amount of alkyl groups at the surfaces.

Effect of enantiomeric excess on surface structures and phase sequences in free-standing liquid-crystal films.

We present differential optical reflectivity and null transmission ellipsometry data from several mixtures of MHPBC enantiomers. From this data, we have determined the chiral smectic phase sequence as a function of enantiomeric excess. The data suggest a change in the structure of the smectic-C(*)(alpha) phase and the surface tilt state as the enantiomeric excess is reduced. The results also show that the intermediate phases, smectic C(*)(FI2), smectic C(*)(FI1), and smectic C(*)(alpha), disappear sequentially on reducing the net chirality.

Unusual thickness-dependent thermal behavior and anticlinic coupling in chiral smectic free-standing liquid-crystal films.

We observe, in free-standing films of a chiral smectic liquid crystal, a series of discrete transitions in the relative orientation of the tilt of the interior and surface layers. These transitions include a remarkable reentrant synclinic-anticlinic-synclinic ordering sequence of the film surfaces in the presence of an electric field upon cooling. The profiles of the associated heat-capacity anomalies are found to be strongly thickness dependent and exhibit a novel crossover behavior in reduced dimensions. We measure the anticlinic coupling between tilted surface layers in the smectic- A phase.

Optical studies of the liquid crystal B2 phase formed by banana-shaped molecules.

Null-transmission ellipsometry and depolarized light microscopy have been performed on free-standing films of three achiral banana-shaped compounds in the B2 phase. Our results support a two-layer unit cell previously proposed to explain the observed antiferroelectricity in thin films and bulk samples. We have studied thicker films than previously reported and have found no deviations in the film structure from the earlier findings. Moreover, we can determine the layer spacing, the molecular tilt from the layer normal, and the three principal indices of refraction in the molecular reference frame.