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Can Fluorinated Molecular Cages Be Utilized as Building Blocks of Hyperhalogens?
Author(s) -
Sun WeiMing,
Li XiangHui,
Li Ying,
Wu Di,
Li ChunYan,
Chen JingHua,
Li ZhiRu
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600052
Subject(s) - superatom , chemistry , dissociation (chemistry) , density functional theory , electron affinity (data page) , molecule , homo/lumo , computational chemistry , fragmentation (computing) , ion , bond dissociation energy , crystallography , chemical physics , organic chemistry , computer science , operating system
Based on the density functional theory for exchange‐correlation potential, fluorocarbon molecular cages are investigated as building blocks of hyperhalogens. By utilizing C 8 F 7 as a ligand, a series of hyperhalogen anions, that is, M(C 8 F 7 ) 2 − (M=Li, Na, and K) and M(C 8 F 7 ) 3 − (M=Be, Mg, and Ca), are modeled. Calculations show that all the C 8 F 7 moieties preserve their geometric and electronic integrity in these anions. These anionic molecules possess larger vertical electron detachment energies (5.11–6.45 eV) than that of C 8 F 7 − , verifying their hyperhalogen nature. Moreover, it is also revealed that using larger fluorinated cage C 10 F 9 as ligands can bring about hyperhalogen anions with larger vertical electron detachment energies. The stability of these studied anions is determined by their large HOMO–LUMO gaps and positive dissociation energies of predetermined possible fragmentation pathways. It is hoped this study will provide an approach for the construction of new types of hyperhalogens and stimulate more research in superatom chemistry.