Size-selected anion photoelectron spectroscopy and theoretical calculations were used to investigate the structural evolution and bonding properties of BSin−/0 (n = 4–12) clusters. The results showed that the B atom in BSi4–12−/0 prefers to occupy the high coordination sites to form more B–Si bonds. The lowest-lying isomers of BSi4–7−/0 primarily adopt bowl-shaped based geometries, while those of BSi8–12−/0 are mainly dominated by prismatic based geometries. For anionic clusters, BSi11− is the critical size of the endohedral structure, whereas BSin neutrals form the B-endohedral structure at n = 9. Interestingly, both anionic and neutral BSi11 have a D3h symmetric tricapped tetragonal antiprism structure with the B atom at the center and exhibit 3D aromaticity. The BSi11− anion possesses σ plus π doubly delocalized bonding characters. The natural population analysis charge distributions on the B atom are related with the structural evolution of BSin− and the B–Si interactions.
Structural evolution and bonding properties of (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations
Sheng-Jie Lu, Xi-Ling Xu, Guo-Jin Cao, Hong-Guang Xu, Wei-Jun Zheng; Structural evolution and bonding properties of (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations. J. Chem. Phys. 7 November 2018; 149 (17): 174314. https://doi.org/10.1063/1.5052559
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