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Excess electron is trapped in a large single molecular cage C 60 F 60
Author(s) -
Wang YinFeng,
Li ZhiRu,
Wu Di,
Sun ChiaChung,
Gu FengLong
Publication year - 2009
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.21310
Subject(s) - cage , electron , chemistry , density functional theory , crystallography , atomic physics , electron density , molecular orbital , molecular physics , computational chemistry , physics , molecule , mathematics , organic chemistry , quantum mechanics , combinatorics
A new kind of solvated electron systems, sphere‐shaped e − @C 60 F 60 ( I h ) and capsule‐shaped e − @C 60 F 60 ( D 6h ), in contrast to the endohedral complex M@C 60 , is represented at the B3LYP/6‐31G(d) + dBF (diffusive basis functions) density functional theory. It is proven, by examining the singly occupied molecular orbital (SOMO) and the spin density map of e − @C 60 F 60 , that the excess electron is indeed encapsulated inside the C 60 F 60 cage. The shape of the electron cloud in SOMO matches with the shape of C 60 F 60 cage. These cage‐like single molecular solvated electrons have considerably large vertical electron detachment energies VDE of 4.95 ( I h ) and 4.67 eV ( D 6h ) at B3LYP/6‐31+G(3df) + dBF level compared to the VDE of 3.2 eV for an electron in bulk water (Coe et al., Int Rev Phys Chem 2001, 20, 33) and that of 3.66 eV for e − @C 20 F 20 (Irikura, J Phys Chem A 2008, 112, 983), which shows their higher stability. The VDE of the sphere‐shaped e − @C 60 F 60 ( I h ) is greater than that of the capsule‐shaped e − @C 60 F 60 ( D 6h ), indicating that the excess electron prefers to reside in the cage with the higher symmetry to form the more stable solvated electron. It is also noticed that the cage size [7.994 ( I h ), 5.714 and 9.978 Å ( D 6h ) in diameter] is much larger than that (2.826 Å) of (H 2 O) 20 − dodecahedral cluster (Khan, Chem Phys Lett 2005, 401, 85). © 2009 Wiley Periodicals, Inc. J Comput Chem 2010