Structures and electronic properties of B3Sin-(n = 4-10) clusters: A combined ab initio and experimental study.
The anionic silicon clusters doped with three boron atoms, B3Sin-(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 B3Sin-(n = 4-10) clusters are globally searched using genetic algorithm incorporated with density functional theory (DFT) calculations. The photoelectron spectra, VDEs, ADEs of these B3Sin-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 B3Sin-(n = 4-10) clusters can be derived by using the squashed pentagonal bipyramid structure of B3Si4-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 B3Si6-and B3Si9-clusters have relatively high stability and enhanced chemical inertness. In particular, the B3Si9-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 1S21P61D102S22P61F14for superatom orbitals.
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Xue
X
Wu
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Sheng-Jie
SJ
Lu
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Xiaoqing
X
Liang
School of Ocean Science and Technology, Dalian University of Technology, Panjin Campus, Panjin 124221, China.
Xiaoming
X
Huang
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Ying
Y
Qin
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Maodu
M
Chen
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Jijun
J
Zhao
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Hong-Guang
HG
Xu
Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602, USA.
R Bruce
RB
King
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Weijun
0000000291362693
W
Zheng