Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (7): 888-895.DOI: 10.6023/A22030109 Previous Articles     Next Articles


碱土金属Ben (n=1~3)对B12团簇结构的调控研究

李海茹a,*(), 张层b, 李思殿c   

  1. a 中北大学朔州校区化学工程与工艺系 山西朔州 036000
    b 中北大学材料科学与工程学院 太原 030051
    c 山西大学分子科学研究所 太原 030031
  • 投稿日期:2022-03-15 发布日期:2022-05-05
  • 通讯作者: 李海茹
  • 基金资助:
    山西省自然科学(青年)基金(201901D211283); 中北大学校基金(XJJ201917)

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

Hairu Lia(), Ceng Zhangb, Sidian Lic   

  1. a Chemical Engineering and Technology, Shuozhou Campus, North University of China, Shuozhou, Shanxi 036000
    b School of Materials Science and Engineering, North University of China, Taiyuan 030051
    c Institute of Molecular Sciences, Shanxi University, Taiyuan 030031
  • Received:2022-03-15 Published:2022-05-05
  • Contact: Hairu Li
  • Supported by:
    Natural Science Foundation of Shanxi Province(201901D211283); School Fund of North China University(XJJ201917)

Based on first-principles, we systematically study the regulation of Ben (n=1~3) on the structure of B12 clusters. For all the low energy isomers of BenB12 (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 Cs symmetry 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 Cs and C2v, 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, Cs BeB12 and Cs Be2B12 are kinetically stable, while some low-energy isomers of C2v Be3B12 can rheology each other. The natural bond orbital (NBO) analysis shows that the clusters Cs BeB12, Cs Be2B12, and C2v 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 BenB12 (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 Cs BeB12 conform to the Hückel (4n+2) rule and is aromatic, while the π bonds of Cs Be2B12, and C2v 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