Polarized Raman Scattering Studies of Orientational Order in Uniaxial Liquid Crystalline Phases
Clark, Noel A.
Priestley, E. B.
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CitationJen, Shen, Noel A. Clark, Peter S. Pershan, and E. B. Priestley. 1977. Polarized Raman scattering studies of orientational order in uniaxial liquid crystalline phases. Journal of Chemical Physics 66(10): 4635-4661.
AbstractThe measurement of vibrational Raman depolarization ratios has been used to study molecular orientational order in uniaxial single domain nematic and smectic liquid crystal samples. This technique is demonstrated to obtain the same microscopic order parameter \(\langle P_2 \rangle =1/2 \langle 3 cos^2\theta −1 \rangle\), where \(\theta\) is the angle between a molecular long axis and the uniaxial direction, as other existing methods. In addition, the next higher moment of the orientational distribution function \(\langle P_4 \rangle=1/8 \langle 35 cos^4 \theta−30 cos^2 \theta+3 \rangle \) has been measured for the first time. The physical basis, theoretical apparatus, and experimental methods necessary for the application of this technique are thoroughly detailed in this paper. Measurements are presented of the temperature dependence of \(\langle P_2 \rangle \) and \(\langle P_4 \rangle \) of N‐(p'‐butoxybenzylidene)‐p‐cyanoaniline (BBCA) dissolved in N‐(p'‐methoxybenzylidene)‐p‐cyanoaniline (MBBA) and of pure MBBA in the isotropic and nematic phases, and in the isotropic, nematic, smectic A, and smectic B phases of N‐(p'‐butoxybenzylidene)‐p‐n‐octylaniline (40.8). In the nematic phases the new quantitative information marks significant discrepancies with existing theories of nematic ordering. In the smectic phases the results show unambiguously the anticipated high degree of molecular orientational order.
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