Chernyshov Ivan Yu, Vener Mikhail V, Shenderovich Ilya G
Department of Quantum Chemistry, D. Mendeleev University of Chemical Technology, Moscow 125047, Russia.
Institute of Organic Chemistry, University of Regensburg, 93053 Regensburg, Germany.
J Chem Phys. 2019 Apr 14;150(14):144706. doi: 10.1063/1.5075519.
The effect of the local structure on the P NMR chemical shift tensor (CST) has been studied experimentally and simulated theoretically using the density functional theory gauge-independent-atomic-orbital approach. It has been shown that the dominating impact comes from a small number of noncovalent interactions between the phosphorus-containing group under question and the atoms of adjacent molecules. These interactions can be unambiguously identified using the Bader analysis of the electronic density. A robust and computationally effective approach designed to attribute a given experimental P CST to a certain local morphology has been elaborated. This approach can be useful in studies of surfaces, complex molecular systems, and amorphous materials.
利用密度泛函理论规范无关原子轨道方法，对局部结构对磷核磁共振化学位移张量（CST）的影响进行了实验研究和理论模拟。结果表明，主要影响来自所研究的含磷基团与相邻分子原子之间的少量非共价相互作用。利用电子密度的巴德分析可以明确识别这些相互作用。已经阐述了一种稳健且计算有效的方法，用于将给定的实验磷CST归因于特定的局部形态。这种方法在表面、复杂分子系统和非晶材料的研究中可能有用。
