Brás A R, Dionísio M, Huth H, Schick Ch, Schönhals A
REQUIMTE/CQFB, Departamento de Química, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
Phys Rev E Stat Nonlin Soft Matter Phys. 2007 Jun;75(6 Pt 1):061708. doi: 10.1103/PhysRevE.75.061708. Epub 2007 Jun 22.
A combination of broadband dielectric (10{-2}Hz-10{9}Hz) and specific heat (10{-3}Hz-2 x 10{3}Hz) spectroscopy is employed to study the molecular dynamics of the glass-forming nematic liquid crystal E7 in a wide temperature range. In the region of the nematic phase the dielectric spectra show two relaxation processes which are expected theoretically: the delta relaxation which corresponds to rotational fluctuations of the molecules around its short axis and the tumbling mode at higher frequencies than the former one. For both processes the temperature dependence of the relaxation rates follows the Vogel-Fulcher-Tammann formula which is characteristic for glassy dynamics. By applying a detailed data analysis, it is shown that close to the glass transition the tumbling mode has a much steeper temperature dependence than the delta process. The former has a Vogel temperature which is by 30K higher than that of the delta relaxation. Specific heat spectroscopy gives one relaxation process in its temperature and frequency dependence which has to be assigned to the alpha relaxation (dynamic glass transition). The unique and detailed comparison of the temperature dependence of the dielectric and the thermal relaxation rates delivers unambiguously that the dielectric tumbling mode has to be related to the dynamic glass transition.
采用宽带介电(10⁻²Hz - 10⁹Hz)和比热(10⁻³Hz - 2×10³Hz)光谱相结合的方法,在很宽的温度范围内研究玻璃态向列型液晶E7的分子动力学。在向列相区域,介电谱显示出两个理论上预期的弛豫过程:对应于分子绕其短轴旋转涨落的δ弛豫,以及频率高于前者的翻滚模式。对于这两个过程,弛豫速率的温度依赖性均遵循玻璃态动力学特征的Vogel - Fulcher - Tammann公式。通过详细的数据分析表明,在接近玻璃化转变时,翻滚模式的温度依赖性比δ过程陡峭得多。前者的Vogel温度比δ弛豫的高30K。比热光谱在其温度和频率依赖性上给出了一个弛豫过程,该过程必须归因于α弛豫(动态玻璃化转变)。对介电弛豫速率和热弛豫速率的温度依赖性进行独特而详细的比较,明确地表明介电翻滚模式与动态玻璃化转变有关。