Influence of Electron Doping on the Hydrogenation of Fullerene C₆₀: A Theoretical Investigation

Abstract

The influence of electron attachment on the stability of the mono- and dihydrogenated buckminsterfullerene C(60) was studied using density functional theory and semiempirical molecular orbital techniques. We have also assessed the reliability of computationally accessible methods that are important for investigating the reactivity of graphenic species and surfaces in general. The B3LYP and M06L functionals with the 6-311+G(d,p) basis set and MNDO/c are found to be the best methods for describing the electron affinities of C(60) and C(60)H(2) . It is shown that simple frontier molecular orbital analyses at both the AM1 and B3LYP/6-31G(d) levels are useful for predicting the most favourable position of protonation of C(60)H(-) , that is, formation of the kinetically controlled product 1,9-dihydro[60]fullerene, which is also the thermodynamically controlled product, in agreement with experimental and previous theoretical studies. We have shown that reduction of exo- and endo-C(60)H makes them more stable in contrast to the reduction of the exo,exo-1,9-C(60)H(2) , reduced forms of which decompose more readily, in agreement with experimental electrochemical studies. However, most other dihydro[60]fullerenes are stabilized by reduction and the regioselectivity of addition is predicted to decrease as the less stable isomers are stabilized more by the addition of electrons than the two most stable ones (1,9 and 1,7).

Doped Polycyclic Aromatic Hydrocarbons as Building Blocks for Nanoelectronics: A Theoretical Study

“…To assess the donor-accepting properties of the species 1 – 5 , we have calculated their ability to attach and detach an electron at the OLYP − /6-311+G(d,p) − ,− ,− level of theory on the ωB97XD/6-31G(d)-optimized geometries. Physicochemical properties calculated with OLYP/6-311+G(d,p) are in good agreement with experiment for a range of organic semiconductors. , On the other hand, large basis sets that include diffuse functions are necessary to describe anions properly …”

“…Physicochemical properties calculated with OLYP/6-311+G(d,p) are in good agreement with experiment for a range of organic semiconductors. 80,81 On the other hand, large basis sets that include diffuse functions are necessary to describe anions properly. 77 As expected, nitrogen behaves as an n-dopant of PAH, and thus, 4 has the lowest electron affinity (EA) and ionization potential (IP) (Table 2).…”

Doping the Buckminsterfullerene by Substitution: Density Functional Theory Studies of C59X (X = B, N, Al, Si, P, Ga, Ge, and As)

“…In the DFT calculations, symmetry constraint is always adopted, and default values of convergence criteria in Gaussian 09 program are used. According to the previous calculations, the B3LYP method has been successfully applied to the theoretical studies on fullerenebased nanostructres [2-5, 8, 13, 23, 27], and the methods used here could give rather good results compared with those obtained by various different functionals and basis sets [33].…”