A high-resolution calorimetric study has been carried out on nanocolloidal dispersions of aerosils in the liquid crystal 4-n-pentylphenylthiol-4'-n-octyloxybenzoate (8S5) as a function of aerosil concentration and temperature spanning the smectic-C to nematic phases. Over this temperature range, this liquid crystal possesses two continuous XY phase transitions: a fluctuation-dominated nematic to smectic-A transition with alpha approximately alphaXY=-0.013 and a mean-field smectic-A to smectic-C transition. The effective critical character of the N-SmA transition remains unchanged over the entire range of the introduced quenched random disorder while the peak height and enthalpy can be well described by considering a cutoff length scale to the quasicritical fluctuations. The robust nature of the N-SmA transition in this system contrasts with cyanobiphenyl-aerosil systems and may be due to the mesogens being nonpolar and having a long nematic range. The character of the SmA-SmC transition changes gradually with increasing disorder but remains mean field like. The heat capacity maximum at the SmA-SmC transition scales as rho with an apparent evolution from tricritical to a simple mean-field step behavior. These results may be generally understood as a stiffening of the liquid crystal (both the nematic elasticity as well as the smectic layer compression modulus B) with silica density.

A variety of 4,4′‐disubstituted phenyl benzoates having a terminal chain containing multifluorine atoms, attached directly to the benzene ring or through an ester group, have been synthesized and their mesomorphic properties determined by hot stage polarizing optical microscopy. These properties were compared to those of the corresponding hydrogenated esters and to other esters containing rigid terminal chains. Usually transition temperatures were higher and mesophase ranges wider than those observed for the parent compounds but no nematic phases were found. Any mesophase seen was usually a smectic A phase sometimes accompanied by a smectic C phase. Crystal E phases were found along with the smectic A phase in alkyl or alkoxy esters having a C9F19CO2 chain on the acid side. A first order smectic A–smectic C transition was observed in the ester with CN on the acid side and O2CC7F15 on the phenol side. A comparison of the effect of a terminal fluorinated chain and a lateral fluorine group on one set of esters is also included.

Small quantities of the floppy bimesogen di(4PPB5)3Si were dissolved in an anticlinic liquid crystal consisting of a mixture of left-handed and right-handed TFMHPOBC, with enantiomer excess X=0.2 . The bimesogen dopant was found to promote anticlinic order with an anticlinic interaction coefficient per molecule udopant smaller than, but of the same order as, that of the rigid bent-core dopant P-7PIMB. For both dopants udopant was found to be much larger than that due to a pair of TFMHPOBC molecules in adjacent layers. The results are examined in terms of both the flexibility of the group linking the two legs of each dopant, as well as their chemical structure.

Small quantities of the bent-core mesogen P-7PIMB were dissolved in an anticlinic liquid crystal consisting of a mixture of left- and right-handed TFMHPOBC, with enantiomer excess X=0.2. The bent-core dopant promotes anticlinic order at higher temperatures, but becomes less effective in suppressing the synclinic phase at the reentrant synclinic transition due to an orientational transition of the dopant within the calamitic TFMHPOBC matrix. Measurements of the anticlinic-synclinic electric-field switching threshold as a function of temperature and dopant concentration facilitate a determination of the component of the anticlinic interaction coefficient U that is due to the bent-core dopant. It is found that the value of U per bent-core molecule is much larger than the corresponding value for a pair of TFMHPOBC molecules in adjacent smectic layers.

A limited selection of ring modified diphenyldiacetylenes of the typewhere A = ,Y =CnH2n+1, CF3, F, COMe, NH2, and NMe2, and A = -[GRAPHICS], trans and cis with Y=F and trans with Y=C3H7, were synthesized. Mesomorphic properties were determined by hot stage polarizing microscopy and DSC. These properties were generally poorer than those found in the parent benzene compounds. This was also true of some pyrimidine analogues reported earlier. Birefringence values also decreased as expected.

A variety of terminal chain modifications (Y) were made on the diacetylenes[GRAPHICS]in which X = CnH2n+1, C12H25O and F, and Y = CH2CH(Me)C2H5, COCH3, C = CC5H11, CnF2n+1 (sic) CnH2n+1 and CH = CHCO2C3H7. Mesomorphic properties were determined by hot stage polarizing microscopy and DSC. These were compared with those for the dialkyl analogues (X = CmH2m+1, Y = CnH2n+1) and a series of 1- and 2-olefins (Y = CH = CHCnH2n+1 and CH2CH = CHCnH2n+1). The 1-olefin series showed wider range nematics than the dialkyl compounds, whereas the above modifications showed either narrow range nematic phases, no mesophase or higher melting temperatures. New transition temperature and enthalpy data are provided for some of the dialkyl and F-alkyl compounds previously reported, for comparisons. Preliminary birefringence data are also included along with the results of some heat and UV stability studies.

Small quantities of the bent-core mesogen P-7PIMB were dissolved in an anticlinic liquid crystal consisting of a mixture of left- and right-handed TFMHPOBC, with enantiomer excess X=0.2. For bent-core concentrations above C=3 wt %, differential scanning calorimetry shows the disappearance of the higher temperature synclinic phase, as well as the appearance of a new peak at a low temperature T c. Polarized infrared absorption measurements indicate that the new DSC peak is due to an orientational transition of the bent-core molecules, analogous to the transition previously observed in a smectic A matrix. For T>T c the plane of the bent-core molecules lies in the tilt plane of the anticlinic matrix, with the arrow (the symmetry axis) of the bent-core molecules parallel to the smectic layers. For T<T c we deduce that the bent-core molecules lie within a single smectic layer, with the polar tilt of the arrow approximately equal to the polar tilt of the TFMHPOBC molecule and the vector connecting the two ends of the bent-core molecule perpendicular to the anticlinic tilt plane. Additionally, T c was found to be an increasing function of bent-core concentration.

The short-range order which remains when the isotropic to smectic- A transition is perturbed by a gel of silica nanoparticles (aerosils) has been studied using high-resolution synchrotron x-ray diffraction. The gels have been created in situ in decylcyanobiphenyl, which has a strongly first-order isotropic to smectic- A transition. The effects are determined by detailed analysis of the temperature and gel density dependence of the smectic structure factor. In previous studies of the continuous nematic to smectic- A transition in a variety of thermotropic liquid crystals the aerosil gel appeared to pin, at random, the phase of the smectic density modulation. For the isotropic to smectic- A transition the same gel perturbation yields different results. The smectic correlation length decreases more slowly with increasing random-field variance in good quantitative agreement with the effect of a random pinning field at a transition from a uniform phase directly to a phase with one-dimensional translational order. We thus compare the influence of random fields on a freezing transition with and without an intervening orientationally ordered phase.

Quasielastic light scattering measurements were performed in the nematic phase of mixtures consisting of the calamitic mesogen 8OCB doped with small concentrations of the bent-core molecule P-7PIMB. It was found that the regular part of the bend elastic constant decreases strongly with dopant concentration X. Close to the nematic-smectic-A phase transition temperature, the divergent part of the bend elastic constant, which is proportional to the bare correlation length xi(0)(||) parallel to the layer normal, also decreases rapidly with X. The effect of the dopant on xi(0)(||) is examined in brief theoretically.

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1–4; and X = C n H2n+1, F, CF3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices. Four of the diacetylenes with m = 1 (A, B = H) were also prepared (X = C6H13, F, n= 2, 3). When X was C6H13 (n=2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X=F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X=C6H13 and n=2 had a melting temperature below room temperature.

The effects of dispersed aerosil nanoparticles on two of the phase transitions of the thermotropic liquid crystal material 4-n-pentylphenylthiol-4'-n-octyloxybenzoate 8barS5 have been studied using high-resolution x-ray diffraction techniques. The aerosils hydrogen bond together to form a gel which imposes a weak quenched disorder on the liquid crystal. The smectic-A fluctuations are well characterized by a two-component line shape representing thermal and random-field contributions. An elaboration on this line shape is required to describe the fluctuations in the smectic-C phase; specifically the effect of the tilt on the wave-vector dependence of the thermal fluctuations must be explicitly taken into account. Both the magnitude and the temperature dependence of the smectic-C tilt order parameter are observed to be unaffected by the disorder. This may be a consequence of the large bare smectic correlation length in the direction of modulation for this transition. These results show that the understanding developed for the nematic to smectic-A transition for octylcyanobiphenyl (8CB) and octyloxycyanobiphenyl (8OCB) liquid crystals with quenched disorder can be extended to quite different materials and transitions.

The electric-field dependence of the velocity of synclinic fingers invading the anticlinic phase is determined by a time-of-flight technique. The time delay for a rapid increase in the transmitted optical intensity through the sample is measured between two points as a function of their separation along the trajectory of the solitary wave. The data are quantitatively consistent with the rapid velocities deduced from a previous measurement [Liq. Cryst. 27, 249 (2000)], demonstrating that the previous data were not affected by multiple nucleation sites occurring at higher fields.

Liquid crystals (LCs) with diazo linkages have high dielectric and optical anisotropy. Two newly synthesized liquid crystalline compounds were dissolved in room temperature LC hosts, E7 and PTTP-24/36, to assess their properties. It was found that these mixtures have higher birefringence, larger dielectric anisotropy, and better elastic properties than the hosts. Satisfactory viscoelastic coefficients were also obtained for these mixtures, showing that they are promising LC materials for applications in the near IR region.

Several alkenyl diphenyldiacetylene liquid crystals were synthesized and their physical properties evaluated. The introduction of a double bond in the side chain leads to an unexpectedly wide nematic range and an extraordinarily large figure of merit at elevated temperatures. These liquid crystals are particularly attractive for infrared laser-beam steering.

A dc electric field was applied perpendicular to the tilt plane of a pitch-compensated (unwound helix) anticlinic liquid crystal. By means of quasielastic light scattering, the field was found to couple the acoustic and optic Goldstone modes, resulting in an increase of the relaxation time tau (beta) of the acousticlike eigenmode. Elastic constants were estimated from the relaxation time data.

The smectic-I(S-I) to smectic-F (S-F) phase transition in terephthal-bis-(4n)-decylaniline (TB10A) has been examined for a possible continuous transition via the intermediate smectic-L (S-L) phase. X-ray diffraction measurements of thick, single-domain, freely suspended films are used to classify the phases and to determine the hexatic order parameter C-6 and its harmonics. Instead of the continuous transition suggested in the literature we find a first-order S-I-->S-F transition with a discontinuous change in the direction of the bond-orientational order relative to the molecular tilt. The tilt of the molecular form factor in the hexatic phases is inconsistent with the tilt estimated from published layer spacing measurements, suggesting that the hexatic phases of TB10A must have the molecular cores oriented at an angle relative to the tails. This result taken together with published results on the S-C phase suggests that the S-C-->S-I-->S-F transitions are driven by changes in the conformation of the hydrocarbon tails. Examination of the harmonic scaling relation between the hexatic order parameters shows mean-field behavior in the S-I phase. This result will make binary mixtures of TB10A with other materials a practical system for the study of the crossover from mean field to the XY behavior seen in other hexatic systems.

Freedericksz measurements were performed on mixtures of a nematic mesogen and a V-shaped molecule. The bend elastic constant was found to decrease significantly with increasing concentration of the V-shaped molecule. The results are discussed theoretically, taking into account the detailed structure of the molecules.

Ring patterns of concentric 2pi solitons in molecular orientation form in freely suspended chiral smectic-C films in response to an in-plane rotating electric field. We present measurements of the driven dynamics of ring formation under conditions of synchronous winding and of the zero-field relaxation of ring patterns, and propose a simple model which enables their quantitative description in low polarization DOBAMBC. In smectic-C*A TFMHPOBC we observe an odd-even layer number effect, with odd layer number films exhibiting order of magnitude slower relaxation rates than even layer films. We show that this rate difference is due to a much larger spontaneous polarization in odd layer number films.

Various substituted aminodiphenyldiacetylenes of the type with X=C3H7,[GRAPHICS]C5H11, F or NO2 and R, R' = H, CH3-C6H13 were synthesized and their mesomorphic properties determined. Semi-empirical and ab initio quantum chemical calculations using AM1, 421G and 631G* suggested that the amino group would increase the dielectric anisotropy and optical birefringence as compared to the alkyl chain. Mesomorphic properties were found to be poor with the maximum nematic phase range being 44.8 degrees C and many of the compounds having no nematic phase. Both melting temperatures and enthalpies for chose having nematic phases were too high to form good eutectic mixtures.

Propagating fingers of synclinic liquid crystalline phase were observed to invade the anticlinic phase for applied electric fields E larger than a characteristic threshold field Eth. The front velocity was found to be highly non-linear in E, with enormous velocities of at least 10 cm s-1, and perhaps as high as 400 cm s-1 for the maximum applied field. These are by far the largest velocities ever observed for a liquid crystal. The results are discussed theoretically, including the possibilities of a field-dependent molecular interaction coefficient and shear thinning.