title: Can Fluorinated Molecular Cages Be Utilized as Building Blocks of Hyperhalogens?
abstract: Based on the density functional theory for exchange-correlation potential, fluorocarbon molecular cages are investigated as building blocks of hyperhalogens. By utilizing C8 F7 as a ligand, a series of hyperhalogen anions, that is, M(C8 F7 )2 (-) (M=Li, Na, and K) and M(C8 F7 )3 (-) (M=Be, Mg, and Ca), are modeled. Calculations show that all the C8 F7 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 C8 F7 (-) , verifying their hyperhalogen nature. Moreover, it is also revealed that using larger fluorinated cage C10 F9 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.
authors.affiliation: Faculty of Pharmacy, Fujian Medical University, Fuzhou, 350108, P. R. China.
authors.forename: Wei-Ming
authors.initials: WM
authors.lastname: Sun
authors.affiliation: Medical Technology and Engineering College, Fujian Medical University, Fuzhou, 350004, P. R. China.
authors.forename: Xiang-Hui
authors.initials: XH
authors.lastname: Li
authors.affiliation: Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P. R. China.
authors.forename: Ying
authors.initials: Y
authors.lastname: Li
authors.affiliation: Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P. R. China. wud@mail.jlu.edu.cn.
authors.forename: Di
authors.initials: D
authors.lastname: Wu
authors.affiliation: Faculty of Pharmacy, Fujian Medical University, Fuzhou, 350108, P. R. China.
authors.forename: Chun-Yan
authors.initials: CY
authors.lastname: Li
authors.affiliation: Faculty of Pharmacy, Fujian Medical University, Fuzhou, 350108, P. R. China. cjh_huaxue@126.com.
authors.forename: Jing-Hua
authors.initials: JH
authors.lastname: Chen
authors.affiliation: Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P. R. China.
authors.forename: Zhi-Ru
authors.initials: ZR
authors.lastname: Li
keywords: density functional calculations; fluorocarbon cages; hyperhalogens; superhalogens; vertical detachment energies