title: Experimental demonstration, using polarized Raman and infrared spectroscopy, that both conventional and de Vries smectic-A phases may exist in smectic liquid crystals with a first-order A-C* transition.
abstract: Two models exist for the orientational distribution of the long molecular axes in smectic-A liquid crystals: the conventional unimodal distribution and the "cone-shaped" de Vries distribution. The de Vries hypothesis provides a plausible picture of how, at a molecular level, a first-order Sm-A to Sm-C* transition may occur, especially if there is little or no concomitant shrinkage of the layer spacing. This work investigates two materials with such transitions: C7 and TSiKN65. The azimuthal distribution of in-layer directors is probed using IR and polarized Raman spectroscopy, which allows us to obtain orientational order parameters. In C7, we observe a discontinuous change in the order parameter, the magnitude of which is small compared with the corresponding change in the in-layer director tilt angle Theta . Assuming that the smectic-A liquid crystal is of the de Vries type, we calculate the Theta required to reproduce the apparent order parameter <P2>app, obtained from IR, by using the true order parameter <P2>, obtained from polarized Raman scattering. The results indicate that, for C7, the tilt angle so calculated is much smaller than that in the Sm-C* angle and hence de Vries behavior may not be the appropriate explanation in this case. Conversely, we find that TSiKN65 shows a different behavior to C7, which can be explained in terms of the de Vries concept. Thus, we conclude that either type of distribution may exist in Sm-A phases which undergo a first-order transition to the Sm-C* phase. We also discuss the changes in the smectic layer spacing and the orientational order parameters across the Sm-A-Sm-C* phase transition, together with changes in birefringence with applied electric field.
authors.affiliation: Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan.
authors.forename: Naoki
authors.initials: N
authors.lastname: Hayashi
authors.forename: A
authors.initials: A
authors.lastname: Kocot
authors.forename: M J
authors.initials: MJ
authors.lastname: Linehan
authors.forename: Atsuo
authors.initials: A
authors.lastname: Fukuda
authors.forename: Jagdish K
authors.initials: JK
authors.lastname: Vij
authors.forename: G
authors.initials: G
authors.lastname: Heppke
authors.forename: J
authors.initials: J
authors.lastname: Naciri
authors.forename: Sachiko
authors.initials: S
authors.lastname: Kawada
authors.forename: Shinya
authors.initials: S
authors.lastname: Kondoh