Nilsson T, Kowalewski J
Division of Physical Chemistry, Stockholm University, Stockholm, S-106 91, Sweden.
J Magn Reson. 2000 Oct;146(2):345-58. doi: 10.1006/jmre.2000.2125.
The slow-motion theory of nuclear spin relaxation in paramagnetic low-symmetry complexes is generalized to comprise arbitrary values of S. We describe the effects of rhombic symmetry in the static zero-field splitting (ZFS) and allow the principal axis system of the static ZFS tensor to deviate from the molecule-fixed frame of the nuclear-electron dipole-dipole tensor. We show nuclear magnetic relaxation dispersion (NMRD) profiles for different illustrative cases, ranging from within the Redfield limit into the slow-motion regime with respect to the electron spin dynamics. We focus on S = 3/2 and compare the effects of symmetry-breaking properties on the paramagnetic relaxation enhancement (PRE) in this case with that of S = 1, which we have treated in a previous paper. We also discuss cases of S = 2, 5/2, 3, and 7/2. One of the main objectives of this investigation, together with the previous papers, is to provide a set of standard calculations using the general slow-motion theory, against which simplified models may be tested. Copyright 2000 Academic Press.
顺磁性低对称配合物中核自旋弛豫的慢动理论被推广到包含任意S值的情况。我们描述了菱形对称性在静态零场分裂（ZFS）中的影响，并允许静态ZFS张量的主轴系统偏离核 - 电子偶极 - 偶极张量的分子固定框架。我们展示了不同示例情况下的核磁共振弛豫色散（NMRD）曲线，范围从处于雷德菲尔德极限内到相对于电子自旋动力学进入慢动区域。我们重点关注S = 3/2的情况，并将这种情况下对称性破缺性质对顺磁弛豫增强（PRE）的影响与我们在前一篇论文中处理的S = 1的情况进行比较。我们还讨论了S = 2、5/2、3和7/2的情况。与之前的论文一起，本研究的主要目标之一是提供一组使用通用慢动理论的标准计算，可据此测试简化模型。版权所有2000年学术出版社。
