Centro de Física e Engenharia de Materiais Avançados, Dept. of Physics, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Phys Chem Chem Phys. 2019 Feb 20;21(8):4523-4537. doi: 10.1039/c8cp06868b.
Molecular order and dynamics of the CB-C9-CB liquid crystalline dimer exhibiting the nematic (N) and the twist bend nematic (Ntb) phases were investigated by proton NMR spectroscopy, using fields of 0.78 T and 7.04 T, and relaxometry. The first relaxometry experiments for a very wide Larmor frequency domain (8 kHz-300 MHz) on this system, using a combination of standard and fast field cycling NMR techniques, were performed. The spectroscopy results in the Ntb phase allowed us to probe the local molecular orientation relative to the Ntb helix axis. The relaxation data were analyzed considering order director fluctuations (ODF), molecular self-diffusion (SD) and local molecular rotations/reorientations (R) relaxation mechanisms. Global fits of theoretical relaxation models, as a function of temperature and Larmor frequency, for the phases under investigation, allowed for the determination of rotational correlation times, diffusion coefficients, viscoelastic parameters, correlation lengths and activation energies (in the case of thermally activated mechanisms). A clear difference between the structures of the N and Ntb phases was detected from the results of proton spin-lattice relaxation through distinct temperature and frequency dependencies' signatures of the collective modes. Significant pre-transitional effects were observed at the N-Ntb phase transition both from relaxometry and spectroscopy data. The experimental results correlate to data and models for comparable liquid crystalline systems.
采用质子 NMR 光谱法,利用 0.78 T 和 7.04 T 的磁场以及弛豫测量法,研究了表现出向列(N)和扭曲向列(Ntb)相的 CB-C9-CB 液晶二聚体的分子有序性和动力学。针对该系统,在非常宽的拉莫尔频率范围内(8 kHz-300 MHz)进行了首次弛豫测量实验,结合了标准和快速场循环 NMR 技术。Ntb 相的光谱结果使我们能够探测局部分子相对于 Ntb 螺旋轴的取向。通过考虑取向序涨落(ODF)、分子自扩散(SD)和局部分子旋转/重定向(R)弛豫机制,对弛豫数据进行了分析。针对所研究的相,对理论弛豫模型的全局拟合,作为温度和拉莫尔频率的函数,确定了旋转相关时间、扩散系数、粘弹性参数、相关长度和活化能(对于热激活机制)。从质子自旋晶格弛豫的结果中可以明显看出 N 和 Ntb 相之间的结构差异,其特征是集体模式的温度和频率依赖性的明显差异。在 N-Ntb 相转变处,从弛豫测量和光谱数据都观察到了显著的预相变效应。实验结果与类似液晶系统的数据和模型相关联。