Fast Field-Cycling NMR Relaxometry Study of Chiral and Nonchiral Nematic Liquid Crystals

被引:23
作者
Sebastiao, P. J. [1 ,5 ]
Gradisek, A. [2 ]
Pinto, L. F. V. [3 ]
Apih, T. [2 ,4 ]
Godinho, M. H. [3 ]
Vilfan, M. [2 ]
机构
[1] Ctr Fis Mat Condensada, P-1649003 Lisbon, Portugal
[2] Jozef Stefan Inst, SI-1000 Ljubljana, Slovenia
[3] UNL, CENIMAT I3N, Dept Ciencia Mat, Fac Ciencias & Tecnol, P-2829516 Caparica, Portugal
[4] EN FIST Ctr Excellence, SI-1000 Ljubljana, Slovenia
[5] Univ Tecn Lisboa, Inst Super Tecn, Dept Phys, P-1049001 Lisbon, Portugal
关键词
NUCLEAR-SPIN RELAXATION; TRANSLATIONAL SELF-DIFFUSION; LATTICE-RELAXATION; MOLECULAR-DYNAMICS; FREQUENCY-DEPENDENCE;
D O I
10.1021/jp206429j
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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-methylpenyl)-4-cyanobiphenyl (5CB*), and a 12% weight mixture of SCB* in 5CB. The proton spin-lattice relaxation time (T-1) 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 T-1(-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 T-1(-1) dispersion is observed at low frequencies. The T-1(-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.
引用
收藏
页码:14348 / 14358
页数:11
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