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Encapsulation Chalcogen Anions in Perfluorinated Silicon Fullerene: X 2− @Si 20 F 20 (X=O, S, Se)
Author(s) -
Wang Hong,
Wu Lin
Publication year - 2011
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201180357
Subject(s) - chemistry , chalcogen , fullerene , crystallography , silicon , atom (system on chip) , density functional theory , atomic radius , cage , endohedral fullerene , computational chemistry , mathematics , organic chemistry , combinatorics , computer science , embedded system
The structures and stabilities of cage Si 20 F 20 and its endohedral complexes X 2− @Si 20 F 20 (X=O, S, Se) were determined at the B3LYP/6‐31G(d) levels of density functional theory (DFT). It is found that the adiabatic electron affinity (EA ad ) of host cage Si 20 F 20 ( I h ) is higher than that of isolated O atom (4.24 vs. 1.46 eV). This suggests the Si 20 F 20 cage can selectively trap and stabilize the capsulated spherical anions. The calculations predict that X=S and Se are nearly located at the center of the cage, and O dramatically deviates from the center in C 3 v symmetry. Moreover, the corresponding X 2− @Si 20 F 20 complexes have more negative inclusion energies (Δ E inc ) and thermodynamic parameters (Δ Z ) than X 2− @C 20 F 20 . The amount of charge that is being transferred from the encapsulated anions to the cage increases with the atomic radius, i.e ., from O 2− ( ca. 45%), S 2− ( ca. 51%) to Se 2− ( ca. 59%), and such a novel model of cage may have practical uses as potential and electrical building units of nanoscale materials.