Binding Energies for Successive Addition Reaction of .OH with C60 : A Laboratory for Testing Frontier Molecular Orbital Theory

TL;DR

This study investigates the regioselectivity and stability of hydroxyl radical addition to C60 fullerenes using density functional theory, revealing charge and orbital control mechanisms and the utility of Fukui functions in predicting reactivity.

Contribution

It provides a detailed analysis of the factors governing regioselectivity in hydroxyl addition to C60, highlighting the role of frontier molecular orbitals and Fukui functions, which advances understanding of fullerene reactivity.

Findings

Hydroxyl addition is under charge and orbital control.

Fukui functions predict reactivity even with zero spin density.

Sign interpretation of dual descriptors varies with calculation type.

Abstract

We study the successive addition reaction of .OH on fullerene C60. We confirm that the lowest energy isomers of C60(OH)n form a belt of hydroxyl groups around the equator of C60, but ask the question of what governs the relative stability of subtitutions at different carbons? Factors concerning regioselectivity are analyzed in terms of conceptual density-functional theory, frontier molecular orbital theory, charge and spin densities, based upon Mulliken population analysis. We confirm that .OH is an electrophilic radical whose successive reaction with C60 is under both charge and orbital control. This is seen to be especially the case for addition to odd .C60(OH)2m+1 fullerenols, but is also seen from a Fukui function and dual descriptor analysis for even C60(OH)2m fullerenols. Of particular interest is the ability of the condensed radical Fukui function f0 to provide information about the reactivity of even C60(OH)2m fullerenols with .OH also when the spin density is zero, and the observation that the interpretation of the sign of the dual descriptor changes depending upon whether a spin-restricted calculation is being performed for even C60(OH)2m fullerenols or a spin-unrestricted calculation is being performed for odd .C60(OH)2m+1 fullerenols.