Quasi-chalcogencharacteristicsof Al12Be: anewsuperatom
It is shown that selected stable clusters can mimic the behavior of atoms in the periodic table and hence canbe regarded as superatoms forming a third dimension of the periodic table.A new kind of superatom,namely Al12Be, that exhibits behaviors reminiscent of chalcogens in theperiodic table, has been proposed in this work.Nine low-lyingAl12Be isomers were primarily obtained and their structuralchanges upon capturing two electrons were subsequently discussed.It is found that the lowest-energy structure of Al12Be is a quasi-icosahedronwith Be atom lying at the center ofthe Al12-cage,and the global minimum of Al12Be2-is a perfect icosahedron conformation with high Ih symmetry.The quasi-chalcogen characteristics of Al12Be is guaranteed bythe prominent stability and electronic behavior of Al12BeLi2 among the Al12BeLin(n =1-5) compounds,the largest highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO) gap of Al12Be2 among Al12BeM (M =Li, Be, B, C, N, O, and F), comparison of the dissociation energies of Al12BeM with those of diatomic MO oxides,similarity between the Al12BeCa/Al12BeFLi3 and CaO/CaScompounds.Finally, the origin of these quasi-chalcogencharacteristics is clarified by analyzing the molecular orbitals of Al12Be,Al12Be2-,and Al12BeLi2 species.We hope this study cannot onlyenrich the superatom chemistry but also provide a novel building block for cluster-assembled materials with tailored properties.
cluster superatom chalcogen molecular orbital theoretical computation
Wei-Ming Sun Ying Li Di Wu Jia-Yuan Liu Zhi-Ru Li
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, Peoples Republic of China
国际会议
昆明
英文
44-57
2014-05-01（万方平台首次上网日期，不代表论文的发表时间）