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

doi:10.6023/A22030109

Abstract

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

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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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Fig. & Tab. 7

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

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

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

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

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

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

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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碱土金属Ben (n=1~3)对B12团簇结构的调控研究