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Pivotal Role of Nonmetal Atoms in the Stabilities, Geometries, Electronic Structures, and Isoelectronic Chemistry of Sc 3 X@C 80 (X = C, N, and O)
Author(s) -
Zhao YaoXiao,
Li MengYang,
Xiong YiMing,
Rahmani Shirin,
Yuan Kun,
Zhao RuiSheng,
Ehara Masahiro,
Nagase Shigeru,
Zhao Xiang
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26049
Subject(s) - chemistry , nonmetal , ab initio , electrophile , computational chemistry , electronic structure , crystallography , nucleophile , atomic orbital , density functional theory , unpaired electron , electron , metal , molecule , biochemistry , physics , organic chemistry , quantum mechanics , catalysis
The thermodynamic and dynamic stabilities of Sc 3 X@C 80 (X = C, N, and O) are explored via density functional theory combined with statistical thermodynamic analysis and ab initio molecular dynamics. It is the first time to comprehensively consider the effect of nonmetal atoms on trimetallic endohedral clusterfullerenes. Relative to Sc 3 X@ I h (31924)‐C 80 (X = N and O) with general six‐electron transfer, an intriguing electronic structure of unexplored Sc 3 C@ D 5 h (31923)‐C 80 with thermodynamic and dynamic stabilities is clearly disclosed. Natural bond orbitals and charge decomposition analysis simultaneously suggest that one unpaired electron appears on the cage for neutral Sc 3 C@ D 5 h (31923)‐C 80 , which could be prospectively stabilized by effective exohedral derivatization and ionization in the future. Moreover, isoelectronic endohedral clusterfullerenes, (Sc 3 C@C 80 ) − , Sc 3 N@C 80 , and (Sc 3 O@C 80 ) + , are also uniquely taken into account. The geometries, electronic structures, reactivities, and reactive sites of isoelectronic species are examined, and it turns out that all the three isoelectronic species would rather electrophilic than nucleophilic reactions. © 2019 Wiley Periodicals, Inc.