Excess electron is trapped in a large single molecular cage C₆₀F₆₀

Abstract

A new kind of solvated electron systems, sphere-shaped e(-)@C60F60 (I(h)) and capsule-shaped e(-)@C60F60 (D6h), in contrast to the endohedral complex M@C60, 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 (D6h) 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 2008, 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 (D6h), 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 A (D6h) in diameter] is much larger than that (2.826 A) of (H2O)20- dodecahedral cluster (Khan, Chem Phys Lett 2005, 401, 85).

Intercage Electron Transfer Driven by Electric Field in Robin–Day‐Type Molecules

“…[19] The resulting single-molecular solvated electron system is more stable than the molecular cluster solvated electron [20] due to the covalent cage acting as a special electron hole. [16] An excess electron can be trapped inside single-molecular double cage C 20 enon in the nonmetal double-cage mixed-valent molecular anion. Herein we report on our search for intercage electron-transfer isomers that show unusual chemical and physical properties and exhibit intercage electron-transfer isomerization pathways, revealing the nature of the electron in the electron-transfer process and enhancing knowledge on isomerism.…”

Electride: from computational characterization to theoretical design

“…Additionally, when alkali metal atoms and superalkali atoms adsorbed on the surface of fluorinated fullerene‐based nanomaterial, C 20 F 20 , the outer electrons of alkali atoms are pulled into the nanocage, and form an electron–hole pair characteristics of M + (e@C 20 F 20 ) − and (M 3 O) + (e@C 20 F 20 ) − (Figure (c)). These closed nanomolecules encapsulating an excess electron are candidates of highly stable NLO materials, which is also true for e@C 60 F 60 (Figure (d)). We notice that this kind of molecular electrides, although have not been successfully synthesized yet, are very promising for applications.…”

“…The Royal Society of Chemistry) and (d) e@C 60 F 60 . (Reproduced with permission from Ref . Copyright 2009.…”

Probing the linear and nonlinear optical properties of nitrogen-substituted carbon nanotube

“…Since the hybrid Becke-style three-parameter exchange functional and the Lee-Yang-Parr correlation functional (B3LYP) is known to yield similar geometries for medium-sized molecules as Møller-Plesset perturbation theory (MP2) calculations do with same basis sets, it has been widely used to optimize the geometries of medium-sized molecules [42][43][44][45][46][47]. Thus, in the present work, the optimized structures of the six N-substituted CNT molecules were obtained at the B3LYP/6-31 g(d) theory level.…”