Experimentalphysik II, Universität Bayreuth, 95440 Bayreuth, Germany.
J Phys Chem A. 2010 Aug 5;114(30):7847-55. doi: 10.1021/jp102498q.
(1)H nuclear magnetic resonance (NMR) field cycling relaxometry has been applied to study the dynamics of homologues of glycerol (propylene glycol, 2,3-butandiol, glycerol, threitol, xylitol, sorbitol) and non-alcohol liquids (o-terphenyl, tristyrene, 3-fluoroaniline, m-toluidine). A broad range of temperatures (200-400 K) is covered, including the supercooled state. From the dispersion of the spin-lattice relaxation rate, R(1)(omega) = T(1)(-1)(omega), the susceptibility representation, omegaT(1)(-1)(omega), has been derived and compared with the susceptibility data from dielectric spectroscopy (DS). The DS spectra can be interpolated by a Cole-Davidson (CD) function, yielding correlation times which are attributed to the structural relaxation (alpha-process) in the supercooled state. In contrast to that, most of the (1)H NMR susceptibility spectra show, in addition to the alpha-relaxation peak, a low-frequency excess contribution with amplitudes varying among the systems. Exceptions are o-terphenyl and tristyrene for which DS and NMR susceptibility curves agree well and both can be reproduced by a CD function. Possible explanations of the low-frequency contribution are discussed. In particular the role of translational diffusion probed via the intermolecular coupling of (1)H spins is considered since it may likely generate the low-frequency excess intensity.
(1) 应用 H 核磁共振 (NMR) 场循环弛豫测量法研究了甘油(丙二醇、2,3-丁二醇、甘油、苏糖醇、木糖醇)和非醇液体(邻三联苯、三聚苯、3-氟苯胺、间甲苯胺)的同系物的动力学。实验涵盖了很宽的温度范围(200-400 K),包括过冷状态。从自旋晶格弛豫率的弥散,R(1)(ω) = T(1)(-1)(ω),推导出了磁化率表示式,ωT(1)(-1)(ω),并与介电谱 (DS) 的磁化率数据进行了比较。DS 谱可以用 Cole-Davidson (CD) 函数进行插值,得到归因于过冷状态结构弛豫(α-过程)的相关时间。与这一点相反,除了 α-松弛峰之外,大多数 (1)H NMR 磁化率谱还显示出低频过剩贡献,其幅度在不同系统之间变化。例外的是邻三联苯和三聚苯,它们的 DS 和 NMR 磁化率曲线吻合得很好,并且都可以用 CD 函数来再现。讨论了低频贡献的可能解释。特别是考虑了通过 (1)H 自旋的分子间耦合探测的平移扩散的作用,因为它可能会产生低频过剩强度。