Finding all‐nonmetal transition‐metal‐like superatom and its magnetic building block

• Published in: International journal of quantum chemistry 2018-07, Vol.118 (13), p.n/a
• Main Authors: Jiang, Hui‐Hui, He, Hui‐Min, Li, Ying, Wu, Di, Liu, Jia‐Yuan, Yang, Hui, Sun, Wei‐Ming, Zhong, Rong-Lin, Zhou, Zhong-Jun, Hou, Jian‐Hua, Wang, Jia‐Jun, Li, Zhi‐Ru
• Format: Article
• Language: English
• Subjects: all‐nonmetal magnetic superatom; all‐nonmetal octahedral cluster; Chemistry; Chlorine; clathrate B6@C60H60; Configurations; Electron spin; Electrons; Jellium; Metal clusters; Molecular chains; Nickel; Physical chemistry; Quantum chemistry; Quantum physics; Size effects; spin moment; transition‐metal
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.25570

In novel superatom chemistry, it is very attractive that all‐metal clusters can mimic the behaviors of nonmetal atoms and simple nonmetal molecules. Wizardly all‐metal halogen‐like superatom Al13 with 2P5 sub shell (corresponding to the 3p5 of chlorine) is the most typical example. In contrast, how to mimic the behaviors of magnetic transition‐metal atom using all‐nonmetal cluster is an intriguing challenge for superatom chemistry. In response to this based on human intuition, using quantum chemistry methods and extending jellium model from metal cluster to all‐nonmetal cluster, we have found out that all‐nonmetal octahedral B6 cluster with characteristic jellium electron configuration 1S21P62S21D8 in the triplet ground state can mimic the behaviors of transition‐metal Ni atom with electron configuration 3s23p64s23d8 in electronic configuration, physics and chemistry. Interestingly, the characteristic order of 1S1P2S1D for the B6 nonmetal cluster with short B‐B lengths is different from that of the traditional jellium model—1S1P1D2S for metal clusters with long M‐M lengths, which exhibits a novel size effect of nonmetal cluster on jellium orbital ordering. Based on the jellium electron configuration, the B6 with the spin moment value of 2μB is a new all‐nonmetal transition‐metal nickel‐like superatom exhibiting a new kind of all‐nonmetal magnetic superatom. Finding the application of the all‐nonmetal magnetic superatom, we encapsulate the magnetic superatom B6 inside fully hydrogenated fullerene forming a clathrate B6@C60H60 with the spin moment value of 2μB. As the C60H60 cage as a polymerization unit can conserve the spin moment of endohedral B6, the clathrate B6@C60H60 is a new all‐nonmetal magnetic superatom building block. Naturally, magnetic superatom structures of the B6 and B6@C60H60 may be metastable. All‐nonmetal octahedral B6 in the triplet ground state is a new all‐nonmetal transition‐metal nickel‐like superatom and it with a spin moment value of 2μB as a new kind of magnetic superatom has been researched in theory for the first time. Meanwhile, B6@C60H60 a new all‐nonmetal magnetic superatom building block has been designed for the first time, as the C60H60 cage can conserve the spin moment of the endohedral B6.