Excess Electron is Trapped in a Large Single Molecular Cage C60F60

A new kind of solvated electron systems, sphere-shaped e(-)@C60F60 (I-h) and capsule-shaped e(-)@C60F60 (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(-)@C60F60, that the excess electron is indeed encapsulated inside the C60F60 cage. The shape of the electron cloud in SOMO matches with the shape of C60F60 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(-)@C20F20 (Irikura, J Phys Chem A 2009, 112, 983), which shows their higher stability. The VDE of the sphere-shaped e(-)@C60F60 (I-h) is greater than that of the capsule-shaped e(-)@C60F60 (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 angstrom (D-6h) in diameter] is much larger than that (2.826 angstrom) of (H2O)(20)(-) dodecahedral cluster (Khan, Chem Phys Lett 2005, 401, 85). (c) 2009 Wiley Periodicals, Inc. J Comput Chem 31: 195-203 2010