Centro de Física da Matéria Condensada, Lisbon, Portugal.
J Phys Chem B. 2011 Dec 15;115(49):14348-58. doi: 10.1021/jp206429j. Epub 2011 Nov 15.
We present a proton NMR relaxometry study of the molecular dynamics in three liquid crystalline systems: 4'-n-pentyl-4-cyanobiphenyl (5CB), (S)-4'-(3-methylpentyl)-4-cyanobiphenyl (5CB*), and a 12% weight mixture of 5CB* in 5CB. The proton spin-lattice relaxation time (T1) was measured as a function of temperature and Larmor frequency in the isotropic, nematic, chiral nematic (N*), and smectic A phases of these liquid crystalline systems. A unified relaxation model was used to analyze the molecular dynamics, considering local molecular rotations/reorientations, translational self-diffusion, and collective motions as the relaxation mechanisms that contribute most effectively to the T1(-1) relaxation. Additionally, in the chiral nematic phase a fourth relaxation mechanism associated with the rotations induced by the translational diffusion along the helical axis (RMTD) was included in the model. All experimental results were consistently analyzed taking into account the physical parameters known for 5CB. The global analysis of the experimental results shows that the RMTDs are associated with the pitch value measured for the N* phases and that its contribution to the T1(-1) dispersion is observed at low frequencies. The T1(-1) dispersion in the smectic A phase of 5CB* is strongly dominated by the layer undulations relaxation mechanism over a broad frequency range from the low kilohertz regime to tens of megahertz. It was the first time such behavior was observed in a low molecular weight liquid crystalline system.
我们呈现了一项质子 NMR 弛豫研究,该研究涉及三种液晶体系中的分子动力学:4'-正戊基-4-氰基联苯(5CB)、(S)-4'-(3-甲基戊基)-4-氰基联苯(5CB*),以及 5CB在 5CB 中的 12%重量混合物。质子自旋晶格弛豫时间(T1)作为温度和拉莫尔频率的函数,在这些液晶体系的各向同性、向列相、手性向列相(N)和近晶 A 相进行了测量。使用统一的弛豫模型来分析分子动力学,该模型考虑了局部分子旋转/重新定向、平移自扩散和集体运动作为对 T1(-1)弛豫最有效的弛豫机制。此外,在手性向列相中,模型中还包括与沿着螺旋轴的平移扩散引起的旋转相关的第四个弛豫机制(RMTD)。所有实验结果都通过考虑已知的 5CB 的物理参数进行了一致分析。实验结果的总体分析表明,RMTDs 与 N* 相测量的螺距值有关,并且在低频下观察到其对 T1(-1)弥散的贡献。5CB*近晶 A 相的 T1(-1)弥散在很宽的频率范围内,从低千赫兹到数十兆赫兹,主要由层起伏弛豫机制主导。这种行为在低分子量液晶体系中尚属首次观察到。