Exploring the Surface Reactivity of 3d Metal Endofullerenes: A Density-Functional Theory Study

Abstract

Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

Theoretical investigation of interactions between palladium and fullerene in polymer

“…For comparison, the calculated HOMO-LUMO gap of the isolated C 60 molecule is 1.64 eV, in very good agreement with other GGA calculations. 56,57 Binding via the [6,6] position increases the band gap by 0.28 eV with respect to that for binding via the [5,6] position.…”

Degradation of methyl salicylate through Cl initiated atmospheric oxidation – a theoretical study

“…where f(r) denotes the sensitivity of electron density r(r) to a change in N electrons system at a constant external potential v. The concept of "the larger the value of the Fukui function, the greater the reactivity" is very useful in explaining the chemical reactivity of many reaction systems. [53][54][55][56][57][58][59][60] In general, the Fukui function has three different forms, f + k , f À k , and f 0 k which govern nucleophilic, electrophilic and radical attacks, respectively. Yang and Mortier 52 proposed a condensed-to-atom form of the Fukui function, where the condensed Fukui functions of the atom k in a molecule with N electrons are expressed as:…”

Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

“…The extrapolation of the general behavior "soft likes soft" and "hard likes hard" locally, together with the idea that the larger the value of the Fukui function, the greater the reactivity, is also a very useful approach to explain the reactivity of many chemical systems. [52][53][54][55][56][57][58] Clearly, the determination of the specific sites at which the interaction between two chemical species will take place is of fundamental significance for the determination of the path and the products of a given reaction. Gázquez et al 59 also stated that the largest value of the Fukui function is generically associated with the most reactive site.…”