1. Structures and electronic properties of B3Sin- (n = 4-10) clusters: A combined ab initio and experimental study.
- Author
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Xue Wu, Sheng-Jie Lu, Xiaoqing Liang, Xiaoming Huang, Ying Qin, Maodu Chen, Jijun Zhao, Hong-Guang Xu, King, R. Bruce, and Weijun Zheng
- Subjects
MOLECULAR clusters ,MOLECULAR structure ,AB initio quantum chemistry methods ,SILICON ,VAPORIZATION - Abstract
The anionic silicon clusters doped with three boron atoms, B
3 Sin - (n = 4-10), have been generated by laser vaporization and investigated by anion photoelectron spectroscopy. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) of these anionic clusters are determined. The lowest energy structures of B3 Sin - (n = 4-10) clusters are globally searched using genetic algorithm incorporated with density functional theory (DFT) calculations. The photoelectron spectra, VDEs, ADEs of these B3 Sin - clusters (n = 4-10) are simulated using B3LYP/6-311+G(d) calculations. Satisfactory agreement is found between theory and experiment. Most of the lowest-energy structures of B3 Sin - (n = 4-10) clusters can be derived by using the squashed pentagonal bipyramid structure of B3 Si4 - as the major building unit. Analyses of natural charge populations show that the boron atoms always possess negative charges, and that the electrons transfer from the 3s orbital of silicon and the 2s orbital of boron to the 2p orbital of boron. The calculated average binding energies, second-order differences of energies, and the HOMO-LUMO gaps show that B3 Si6 - and B3 Si9 - clusters have relatively high stability and enhanced chemical inertness. In particular, the B3 Si9 - cluster with high symmetry (C3v ) stands out as an interesting superatom cluster with a magic number of 40 skeletal electrons and a closed-shell electronic configuration of 1S²1P6 1D10 2S²2P6 1F14 for superatom orbitals. [ABSTRACT FROM AUTHOR]- Published
- 2017
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