碱土金属Ben (n=1~3)对B12团簇结构的调控研究

doi:10.6023/A22030109

摘要/Abstract

基于第一性原理, 系统地研究了Be_n (n=1~3)对B₁₂团簇结构的调控. 结果表明: 团簇BeB₁₂全局极小结构为C_s对称性准平面结构, 而Be₂B₁₂和Be₃B₁₂最稳定的结构均为笼状结构, 对称性分别为C_s和C₂_v. 随着Be_n (n=1~3)原子数的增加, 团簇B₁₂由准平面结构过渡到笼状结构, 且Be倾向内嵌在B₁₂笼状结构表面的B₇或B₈单元环中, 通过离子和共价作用形成稳定Be&B₇和Be&B₈单元, 从而稳定笼状结构. 自然键轨道(NBO)分析表明, 团簇C_s BeB₁₂, C_s Be₂B₁₂, C₂_v Be₃B₁₂内部存在电子转移情况, Be原子2s轨道上失去电子, Be—B键主要以离子作用为主, 同时也存在共价作用. 成键分析显示C_s Be₂B₁₂和C₂_v Be₃B₁₂的π键遵循球状芳香性2(n+1)² (n=1)电子计数规则, 表明该团簇具有球状芳香性. 预测了三个结构的红外和拉曼光谱, 为以后的合成实验和数据表征提供了理论基础.

关键词: 硼团簇, 金属掺杂, 第一性原理, 成键分析, 动力学模拟, 光谱模拟

Based on first-principles, we systematically study the regulation of Be_n (n=1~3) on the structure of B₁₂ clusters. For all the low energy isomers of Be_nB₁₂ (n=1~3) searched at the PBE/DZVP level, we further use PBE0 and TPSSh methods to calculate their relative energy and select the most optimal structure, and then calculate its single point energy at CCSD(T)/6-311+G(d). The results show that the global minimum structure of BeB₁₂ is quasi-planar and has C_ssymmetry at the CCSD(T)/6-311+G(d) level. However, the most stable structures of Be₂B₁₂ and Be₃B₁₂ are cage-like structures, and their symmetries are C_s and C₂_v, respectively. Subsequently, with the increase of the number of Be atoms, B₁₂ has a dramatic transition from quasi-planar structure to cage-like structure, and Be atoms tend to be embedded in the B₇ or B₈ unit ring on the surface of the cage-like structure of B₁₂, forming stable Be&B₇ and Be&B₈ units through ionic and covalent interaction to stabilize the cage-like structure. Furthermore, at 400 K, C_s BeB₁₂ and C_s Be₂B₁₂ are kinetically stable, while some low-energy isomers of C₂_v Be₃B₁₂ can rheology each other. The natural bond orbital (NBO) analysis shows that the clusters C_s BeB₁₂, C_s Be₂B₁₂, and C₂_v Be₃B₁₂ have obvious electron transfer, and the 2s orbital of Be atom loses electrons. And the Be—B bonds are mainly ionic, covalent bonds exist at the same time. Adaptive natural density partitioning (AdNDP) reveals the bonding pattern of Be_nB₁₂ (n=1~3), and we find that both the σ bonds and the multicenter π bonds promote the stability of the whole molecule. The results indicate that the π bonds of C_s BeB₁₂ conform to the Hückel (4n+2) rule and is aromatic, while the π bonds of C_s Be₂B₁₂, and C₂_v Be₃B₁₂ follow the spherical aromatic 2(n+1)² (n=1) electron counting rule, with spherical aromaticity. In addition, we also predict the infrared and Raman spectra of the three structures in this text, which will provide theoretical basis for the experimentally synthesis and characterization of these structures in the future.

Key words: boron clusters, metal doped, first-principles theory, bonding analysis, MD simulation, spectra simulation

引用此文

李海茹, 张层, 李思殿. 碱土金属Be_n (n=1~3)对B₁₂团簇结构的调控研究[J]. 化学学报, 2022, 80(7): 888-895.

Hairu Li, Ceng Zhang, Sidian Li. Study on the Regulation of Alkali-earth Metal Be_n (n=1~3) on the Structure of B₁₂ Clusters[J]. Acta Chimica Sinica, 2022, 80(7): 888-895.

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图/表 7

图1. BenB12 (n=1~3)在CCSD(T), PBE0和TPSSh/6-311+G(d)水平下得到的全局极小结构及低能量异构体: (a) Cs BeB12; (b) Cs Be2B12; (c) C2v Be3B12

Figure 1. Global minimal structure and low-energy isomers of BenB12 (n=1~3) at CCSD (T), PBE0 and TPSSh levels with 6-311+G(d): (a) Cs BeB12; (b) Cs Be2B12; (c) C2v Be3B12

图2. (a) Cs BeB12, (b) Cs Be2B12及(c) C2v Be3B12结构在400 K下的分子动力学模拟, 时间为30 ps (a) Cs BeB12, (b) Cs Be2B12及(c) C2v Be3B12结构在400 K下的分子动力学模拟, 时间为30 ps

Figure 2. Molecular dynamics simulations of (a) Cs BeB12, (b) Cs Be2B12 and (c) C2v Be3B12 at 400 K for 30 ps

	BeB₁₂	Be₂B₁₂	Be₃B₁₂
B—B键长范围	0.155~0.183	0.153~0.187	0.151~0.196
B—Be键长范围	0.185~0.206	0.191~0.225	0.188~0.216
Be—Be键长范围	—	0.240	0.261~0.269
Be—B WBIs	0.01~0.17	0.01~0.15	0.02~0.17
Be—Be WBIs	0.00	0.00~0.01	0.00~0.01
B价电子构型	2s^0.65–0.932p^2.05–2.81	2s^0.60–0.892p^2.09–2.86	2s^0.80–0.872p^2.44–2.67
Be价电子构型	2s^0.212p^0.19	2s^0.222p^0.15	2s^0.16–0.282p^0.15–0.16

表1. 在PBE0/6-311+G(d)水平下的Cs BeB12, Cs Be2B12和C2v Be3B12键长(in nm)、韦伯键级及电子构型

Table 1. Calculated bond distances (in nm), WBIs and electronic configurations of Cs BeB12, Cs Be2B12 and C2v Be3B12 clusters at the PBE0/6-311+G(d) level

图3. PBE0/6-311+G(d)水平下, 团簇Cs BeB12, Cs Be2B12及C2v Be3B12 GM结构的NBO电荷

Figure 3. NBO charges (in |e|) at the PBE0/6-311+G(d) level for the GM structures of Cs BeB12, Cs Be2B12 and C2v Be3B12 clusters

图4. 团簇Cs BeB12 (a), Cs Be2B12 (b)及C2v Be3B12 (c)的π分子轨道图

Figure 4. The π molecular orbitals of Cs BeB12 (a), Cs Be2B12, (b) and C2v Be3B12 (c)

图5. Cs Be2B12的AdNDP分析, ON代表占据数

Figure 5. AdNDP analyses of Cs Be2B12, the occupation numbers (ONs) are indicated

图6. (a) Cs BeB12, (b) Cs Be2B12和(c) C2v Be3B12的红外光谱图

Figure 6. Infrared spectra of (a) Cs BeB12, (b) Cs Be2B12 and (c) C2v Be3B12

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碱土金属Be_n (n=1~3)对B₁₂团簇结构的调控研究

Study on the Regulation of Alkali-earth Metal Be_n (n=1~3) on the Structure of B₁₂ Clusters

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