Shi Xiaofei, Song Jinshuai, Wei Donghui
College of Chemistry, and Pingyuan Laboratory, Zhengzhou University, Zhengzhou, 450001, PR China.
Nat Commun. 2025 Mar 27;16(1):3013. doi: 10.1038/s41467-025-58281-9.
An analysis method with the name of the Projection of Orbital Coefficient Vector (POCV) has been proposed for predicting π electronic properties, aromaticity, and the directional reactivity of molecules including reactivity vectors. This approach significantly differs from previous computational methods by explicitly accounting for orbital overlap directions. Using the POCV method, accurate predictions of π electron properties and directional reactivity indices have been successfully demonstrated across various unsaturated molecules. To illustrate the advantages of POCV over conventional methods, we present several case studies involving the computation of π electron properties and reactivity vectors for diverse molecular systems, including non-planar axially chiral molecules, nucleophilic and electrophilic carbenes, and linear conjugated molecules. Here we show, the POCV method enables accurate prediction of chemical reaction sites with multiple orbital overlap directions, and facilitates the calculations of π electron properties.
一种名为轨道系数向量投影（POCV）的分析方法已被提出，用于预测包括反应性向量在内的分子的π电子性质、芳香性和方向反应性。该方法通过明确考虑轨道重叠方向，与以前的计算方法有显著不同。使用POCV方法，已成功地在各种不饱和分子中对π电子性质和方向反应性指数进行了准确预测。为了说明POCV相对于传统方法的优势，我们展示了几个案例研究，涉及计算各种分子体系的π电子性质和反应性向量，包括非平面轴向手性分子、亲核和亲电卡宾以及线性共轭分子。在此我们表明，POCV方法能够准确预测具有多个轨道重叠方向的化学反应位点，并有助于π电子性质的计算。
