Elucidation of the de Vries behavior in terms of the orientational order parameter, apparent tilt angle, and field-induced tilt angle for smectic liquid crystals by polarized infrared spectroscopy.

We report experimental results of the orientational order parameter, the apparent tilt angle, and the field-induced tilt angle for three chiral smectic liquid crystalline materials investigated using infrared (IR) polarized spectroscopy. The common feature in these materials is use of the core 5-methyl-2- pyrimidine benzoate as the central part of the mesogen. This core is terminated by siloxane or carbosilane chains on one of the ends and by the chiral alkoxy chains on the opposite. These compounds exhibit low concomitant layer shrinkage at the smectic A^{*} (SmA^{*}) to smectic C^{*} (SmC^{*}) transition temperature and within the SmC^{*} phase itself. The maximum layer shrinkage in SmC^{*} is observed as ∼1.5%. We calculate the apparent orientational order parameter, S_{app} in the laboratory reference frame from the observed IR absorbance for homeotropic aligned samples, and the true order parameter, S, is calculated using the measured tilt angle and is also interpolated from Iso-SmA^{*} transition temperature closer to SmC^{*} phase. The apparent tilt angle in the SmA^{*} phase calculated from a comparison of order parameters S and S_{app} is found to be significantly large. A low magnitude of S_{app} found for homeotropic aligned samples in the SmA^{*} phase indicates that the order parameter plays a vital role in determining the de Vries characteristics, especially of exhibiting larger apparent tilt angles. Furthermore there is a significant increase in the true order parameter at temperatures close to SmA^{*} to SmC^{*} transition temperature in all three compounds. The planar-aligned samples are used to study the dependence of induced tilt angle on the applied electric field. The generalized Langevin-Debye model given by Shen et al. reasonably fits the experimental data on the field-induced tilt angle. The results show that the dipole moment of the tilt correlated domain in SmA^{*} diverges as temperature is lowered to the SmA^{*}-SmC^{*} transition temperature. The generalized Langevin-Debye model is also found to be extremely effective in confirming some of the conclusions of the de Vries behavior.