Citation: Huang Min, Xu Chang, Cheng Longjiu. Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)[J]. Acta Chimica Sinica, ;2016, 74(9): 758-763. doi: 10.6023/A16050230 shu

Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)

1.
School of Chemistry and Chemical Engineering, Anhui University, Hefei 260301

Corresponding author: Cheng Longjiu, clj@ustc.edu
Received Date: 11 May 2016

Fund Project: National Natural Science Foundation of China 21273008National Natural Science Foundation of China 21573001

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In this paper, the global minimum search and structural optimization for the B-Al binary clusters [B_xAl₁₃_-_x]^- (x=0～13) are performed using the genetic algorithm (GA) method coupled with density functional theory (DFT). The effects of composition on the atomic structures, electronic properties including the energy gaps and vertical detachment energies of B-Al binary clusters are discussed. The results distinctly reveal a three dimensional (3D) to (quasi-)planar (2D) structural transition as a function of x upon increasing the number of boron atoms. When x is in the range of 0 to 7, the clusters are Al-rich and the B-Al binary systems maintain the 3D structure. Whereas, the binary system trends to be quasi-planar structure, and the critical B:Al ratios for the 2D-3D transition are between x=7 and 8. To study the stability of the [B_xAl_13-x]^- clusters, we defined the relative energy (E_rel=E([B_xAl₁₃_-x]^-)-xE(B₁₃^-)/13–yE(Al₁₃^-)/13), where the cluster with a more negative E_rel is more stable. At x=1, E_rel is the most negative, indicating the highest stability. In order to further understand the stability of clusters, the vertical detachment energies (VDE) and the HOMO-LUMO energy gaps (E_H-L) of [B_xAl₁₃_-_x]^- (x=0～13) clusters are also calculated. The results show that the energy decreases with the increasing number of B atoms, indicating a lower stability. The largest E_H-L of BAl₁₂^- cluster indicates that it is the most stable among all the series of this clusters. Molecular orbitals (MO) of BAl₁₂^- cluster are analyzed and the result shows that the electronic shells of 1s² and 1p⁶ are virtually unchanged when the central Al atom is replaced by the B atom. It also indicates that the electron shell closing model could be regarded as a simple but valid tool for explaining the structures and stabilities of metal clusters. Chemical bonding analysis by Adaptive Natural Density Partitioning (AdNDP) method for the B₁₃^- cluster reveals that it is a π-antiaromatic system with 8 delocalized π-electrons.
- density functional theory,
- [B_xAl₁₃_-x]^- (x=0～13) clusters,
- optimization,
- molecular orbitals,
- adaptive natural density partitioning
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Density Functional Theory Studies of the Binary Systems[BxAl13-x]- (x=0～13)

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通讯作者: 陈斌, bchen63@163.com

Density Functional Theory Studies of the Binary Systems[B_xAl₁₃_-x]^- (x=0～13)