Bogoslovov R B, Roland C M, Czub J, Urban S
Chemistry Division, Code 6120, Naval Research Laboratory, Washington, DC 20375-5342, USA.
J Phys Chem B. 2008 Dec 18;112(50):16008-11. doi: 10.1021/jp805421g.
Pressure-volume-temperature (PVT) measurements were carried out on the nematic liquid crystal 4(trans-4'-n-hexylcyclohexyl)isothiocyanatobenzene (6CHBT). In combination with previous dielectric relaxation measurements at elevated pressure and new measurements extending to GHz frequencies, the characteristics of the anisotropic interaction potential were determined. The thermodynamic potential parameter, gamma, which measures the variation of the interaction energy with volume, equals 5.03 +/- 0.06, with a barrier height equal to approximately 7 kJ/mol. Thus, there is a low potential barrier to reorientations of the 6CHBT molecule about its short axis; however, the retarding potential is strongly volume-dependent. The longitudinal reorientational times determined for various thermodynamic conditions superpose using a scaling exponent equal to gamma within the experimental error. It then follows, as found recently for other liquid crystals, that this relaxation time must be constant along the pressure-dependent clearing line. Thus, the control parameter (e.g., Gibbs free energy) governing the competition between the anisotropic energy and the entropy must also govern the rotational dynamics in the ordered phase of this liquid crystal.
对向列型液晶4-(反式-4'-正己基环己基)异硫氰酸苯酯(6CHBT)进行了压力-体积-温度(PVT)测量。结合先前在高压下进行的介电弛豫测量以及扩展到吉赫兹频率的新测量,确定了各向异性相互作用势的特征。衡量相互作用能随体积变化的热力学势参数γ等于5.03±0.06,势垒高度约为7 kJ/mol。因此,6CHBT分子绕其短轴重新取向存在低势垒;然而,阻滞势强烈依赖于体积。在实验误差范围内,使用等于γ的标度指数可使在各种热力学条件下确定的纵向重取向时间叠加。然后可以得出,正如最近在其他液晶中发现的那样,沿着压力依赖的清亮点线,该弛豫时间必须是恒定的。因此,控制各向异性能量与熵之间竞争的控制参数(例如吉布斯自由能)也必须控制该液晶有序相中的旋转动力学。