TY - JOUR
T1 - Orientational order parameters of a de Vries–type ferroelectric liquid crystal obtained by polarized Raman spectroscopy and x-ray diffraction
AU - Sanchez-Castillo, A.
AU - Osipov, Mikhail A.
AU - Jagiella, S.
AU - Nguyen, Z.H.
AU - Kaspar, M.
AU - Hamplova, V.
AU - Maclennan, J.
AU - Giesselmann, F.
PY - 2012/6/11
Y1 - 2012/6/11
N2 - The orientational order parameters 〈P2〉 and 〈P4〉 of the ferroelectric, de Vries–type liquid crystal 9HL have been determined in the SmA* and SmC* phases by means of polarized Raman spectroscopy, and in the SmA* phase using x-ray diffraction. Quantum density functional theory predicts Raman spectra for 9HL that are in good agreement with the observations and indicates that the strong Raman band probed in the experiment corresponds to the uniaxial, coupled vibration of the three phenyl rings along the molecular long axis. The magnitudes of the orientational order parameters obtained in the Raman and x-ray experiments differ dramatically from each other, a discrepancy that is resolved by considering that the two techniques probe the orientational distributions of different molecular axes. We have developed a systematic procedure in which we calculate the angle between these axes and rescale the orientational order parameters obtained from x-ray scattering with results that are then in good agreement with the Raman data. At least in the case of 9HL, the results obtained by both techniques support a “sugar loaf” orientational distribution in the SmA* phase with no qualitative difference to conventional smectics A. The role of individual molecular fragments in promoting de Vries–type behavior is considered.
AB - The orientational order parameters 〈P2〉 and 〈P4〉 of the ferroelectric, de Vries–type liquid crystal 9HL have been determined in the SmA* and SmC* phases by means of polarized Raman spectroscopy, and in the SmA* phase using x-ray diffraction. Quantum density functional theory predicts Raman spectra for 9HL that are in good agreement with the observations and indicates that the strong Raman band probed in the experiment corresponds to the uniaxial, coupled vibration of the three phenyl rings along the molecular long axis. The magnitudes of the orientational order parameters obtained in the Raman and x-ray experiments differ dramatically from each other, a discrepancy that is resolved by considering that the two techniques probe the orientational distributions of different molecular axes. We have developed a systematic procedure in which we calculate the angle between these axes and rescale the orientational order parameters obtained from x-ray scattering with results that are then in good agreement with the Raman data. At least in the case of 9HL, the results obtained by both techniques support a “sugar loaf” orientational distribution in the SmA* phase with no qualitative difference to conventional smectics A. The role of individual molecular fragments in promoting de Vries–type behavior is considered.
KW - Ferroelectric liquid crystal
KW - raman spectra
KW - orientational order parameters
KW - x-ray scattering
UR - http://www.scopus.com/inward/record.url?scp=84862185555&partnerID=8YFLogxK
U2 - 10.1103/PhysRevE.85.061703
DO - 10.1103/PhysRevE.85.061703
M3 - Article
SN - 1539-3755
VL - 85
JO - Physical Review E: Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
JF - Physical Review E: Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
IS - 6
M1 - 061703
ER -