Analysis of Electric Field Gradient Tensors at Quadrupolar Nuclei in Common Structural Motifs
Analysis of Electric Field Gradient Tensors at Quadrupolar Nuclei in Common Structural Motifs
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DOI：
10.1002/cmr.a.20155
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发表时间：
2010-03-01
影响因子：
0.6
通讯作者：
Schurko, Robert W.
中科院分区：
文献类型：
--
作者：
Autschbach, Jochen;Zheng, Shaohui;Schurko, Robert W.
本文关注的是电场梯度（EFG）的分析，使用第一性原理理论沿着与模型计算。简单的原子轨道（AO）模型的EFG的汤斯-戴利（TD）分析的精神和适用于各种集的sp（n）杂化轨道和原子d轨道壳。这些AO模型，然后结合现代分析方法植根于第一原理理论，提供准确的本地化的分子轨道贡献的EFG。密度泛函计算表明，这种分析的EFG的各种典型的结构图案可以提供一个直观的方式来理解的化学起源的EFG张量的大小和符号在原子核，以及它们的方向相对于分子的坐标系。EFG张量的图形可视化的效用也被强调。被调查的系统的范围从非常小的分子（碳和硫的EFG在CO，CS，OCS）的小型和中型分子（氮和铝的EFG在氨，甲基氰化物和异氰化物，铝AlX 3模型系统和各种铝有机系统），过渡金属络合物与Ru和Nb和各种配体的金属原子场梯度。(C)2010 Wiley Periodicals，Inc. Concepts Magn Reson Part A 36A：84-126，2010.
This article is concerned with the analysis of electric field gradients (EFGs) using first principles theory along with model calculations. Simple atomic orbital (AO) models for the EFG are developed in the spirit of the Townes-Dailey (TD) analysis and applied to various sets of sp(n) hybrid orbitals and to atomic d orbital shells. These AO models are then combined with modern analysis methods rooted in first principles theory which provide accurate localized molecular orbital contributions to the EFG. It is shown by density functional computations how such analyses of the EFG for a variety of typical structural motifs can provide an intuitive way of understanding the chemical origin of the magnitude and the sign of EFG tensors at atomic nuclei, as well as of their orientation with respect to the molecular coordinate frame. The utility of graphical visualizations of EFG tensors is also emphasized. The systems that are investigated span the range from very small molecules (carbon and sulfur EFGs in CO, CS, OCS) to small- and medium-sized molecules (nitrogen and aluminum EFGs in ammonia, methyl-cyanide and -isocyanide, aluminum AlX3 model systems and various alumino-organic systems), to the metal atom field gradient in transition metal complexes with Ru and Nb and a variety of ligands. (C) 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 84-126, 2010.