金属中心四面体六面体V⁺团簇的结构、电子和磁性性质的第一性原理研究

Li Xiaojun, Ren Hongjiang, Huang Xinwei, Li Shuna

The Key Laboratory for Surface Engineering and Remanufacturing in Shaanxi Province, School of Chemical Engineering, Xi'an University, Xi'an 710065, China.

Nanomaterials (Basel). 2017 Jun 30;7(7):164. doi: 10.3390/nano7070164.

The V-centered bicapped hexagonal antiprism structure (), as the most stable geometry of the cationic V⁺ cluster, is determined by using infrared multiple photo dissociation (IR-MPD) in combination with density functional theory computations. It is found that the structure can be stabilized by 18 delocalized 3c-2e σ-bonds on outer V₃ triangles of the bicapped hexagonal antiprism surface and 12 delocalized 4c-2e σ-bonds on inner trigonal pyramidal V₄ moiety, and the features are related to the strong - hybridization of the cluster. The total magnetic moments on the cluster are predicted to be 2.0 , which come mainly from the central vanadium atom.

作为阳离子V⁺团簇最稳定的几何结构，V中心双帽六角反棱柱结构（）是通过红外多光子解离（IR-MPD）结合密度泛函理论计算确定的。研究发现，该结构可通过双帽六角反棱柱表面外部V₃三角形上的18个离域3c-2e σ键和内部三角锥V₄部分上的12个离域4c-2e σ键得以稳定，这些特征与团簇的强 - 杂化有关。团簇上的总磁矩预计为2.0，主要来自中心钒原子。