Sheong Fu Kit, Zhang Jing-Xuan, Lin Zhenyang
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China.
J Chem Theory Comput. 2024 Aug 13;20(15):6569-6577. doi: 10.1021/acs.jctc.4c00456. Epub 2024 Jul 24.
In chemical research, it is a common practice to carry out quantum chemical calculations and analyze the canonical molecular orbitals (CMOs) obtained to study electronic structures of chemical systems. However, extensive orbital mixing of CMOs especially in molecular clusters significantly complicates our understanding of the electronic structures. In this paper, we have developed an innovative tool called fragment aligned molecular orbital (FAMO) analysis, which reconstructs our modular chemical picture by making use of the Procrustes analysis in statistical theory to align the occupied molecular orbitals of a molecular species against the occupied (molecular) orbitals of the constituting fragments of the cluster, and results in a set of chemically intuitive semilocalized orbitals. This alignment technique minimizes the extensive orbital mixing, thus allowing precise observation of bonding interactions in complex chemical systems. A few representative clusters have been selected as showcase examples to demonstrate the advantage of FAMO analysis in deciphering the distinct bonding interactions in cluster compounds.
在化学研究中，进行量子化学计算并分析所得的正则分子轨道（CMO）以研究化学体系的电子结构是一种常见的做法。然而，CMO的广泛轨道混合，尤其是在分子簇中，极大地复杂化了我们对电子结构的理解。在本文中，我们开发了一种名为片段对齐分子轨道（FAMO）分析的创新工具，它利用统计理论中的普罗克汝斯忒斯分析，将分子物种的占据分子轨道与簇的组成片段的占据（分子）轨道对齐，从而重构我们的模块化化学图景，并得到一组具有化学直观性的半定域轨道。这种对齐技术最大限度地减少了广泛的轨道混合，从而能够精确观察复杂化学体系中的键合相互作用。我们选择了一些具有代表性的簇作为展示示例，以证明FAMO分析在解读簇化合物中独特键合相互作用方面的优势。
