In:
International Journal of Quantum Chemistry, Wiley, Vol. 118, No. 13 ( 2018-07-05)
Abstract:
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 Al 13 with 2P 5 sub shell (corresponding to the 3p 5 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 B 6 cluster with characteristic jellium electron configuration 1S 2 1P 6 2S 2 1D 8 in the triplet ground state can mimic the behaviors of transition‐metal Ni atom with electron configuration 3s 2 3p 6 4s 2 3d 8 in electronic configuration, physics and chemistry. Interestingly, the characteristic order of 1S1P2S1D for the B 6 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 B 6 with the spin moment value of 2μ B 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 B 6 inside fully hydrogenated fullerene forming a clathrate B 6 @C 60 H 60 with the spin moment value of 2μ B . As the C 60 H 60 cage as a polymerization unit can conserve the spin moment of endohedral B 6 , the clathrate B 6 @C 60 H 60 is a new all‐nonmetal magnetic superatom building block. Naturally, magnetic superatom structures of the B 6 and B 6 @C 60 H 60 may be metastable.
Type of Medium:
Online Resource
ISSN:
0020-7608
,
1097-461X
Language:
English
Publisher:
Wiley
Publication Date:
2018
detail.hit.zdb_id:
1475014-4
