Definite existence of subphases with eight- and ten-layer unit cells as studied by complementary methods, electric-field-induced birefringence and microbeam resonant x-ray scattering.

A mixture of two selenium-containing compounds, 80 wt. % AS657 and 20 wt. % AS620, are studied with two complementary methods, electric-field-induced birefringence (EFIB) and microbeam resonant x-ray scattering (μRXS). The mixture shows the typical phase sequence of Sm-C_{A}^{*}-1/3-1/2-Sm-C^{*}-Sm-C_{α}^{*}-Sm-A, where 1/3 and 1/2 are two prototypal ferrielectric and antiferroelectric subphases with three- and four-layer unit cells, respectively. Here we designate the subphase as its q_{T} number defined by the ratio of [F]/([F]+[A]), where [F] and [A] are the numbers of synclinic ferroelectric and anticlinic antiferroelectric orderings in the unit cell, respectively. The electric field vs temperature phase diagram with EFIB contours indicates the emergence of three additional subphases, an antiferroelectric one between Sm-C_{A}^{*} and 1/3 and antiferroelectric and apparently ferrielectric ones between 1/3 and 1/2. The simplest probable q_{T}'s for these additional subphases are 1/4, 2/5, and 3/7, respectively, in the order of increasing temperature. The μRXS profiles indicate that antiferroelectric 1/4 and 2/5 approximately have the eight-layer (FAAAFAAA) and ten-layer (FAFAAFAFAA) Ising unit cells, respectively. The remaining subphase may be ferrielectric 3/7 with a seven-layer unit cell, although the evidence is partial. These experimental results are compared with the phenomenological Landau model [P. V. Dolganov and E. I. Kats, Liq. Cryst. Rev. 1, 127 (2014)2168-039610.1080/21680396.2013.869667] and the quasimolecular model [A. V. Emelyanenko and M. A. Osipov, Phys. Rev. E 68, 051703 (2003)1063-651X10.1103/PhysRevE.68.051703].