Interaction between alkyl radicals and single wall carbon nanotubes

The addition of primary, secondary, and tertiary alkyl radicals to single wall carbon nanotubes (SWCNTs) was studied by means of dispersion corrected density functional theory. The PBE, B97‐D, M06‐L, and M06‐2X functionals were used. Consideration of Van der Waals interactions is essential to obtain accurate addition energies. In effect, the enthalpy changes at 298 K, for the addition of methyl, ethyl, isopropyl, and tert‐butyl radicals onto a (5,5) SWCNT are: ?25.7, ?25.1, ?22.4, and ?16.6 kcal/mol, at the M06‐2X level, respectively, whereas at PBE/6‐31G* level they are significantly lower: ?25.0, ?19.0, ?16.7, and ?5.0 kcal/mol respectively. Although the binding energies are small, the attached alkyl radicals are expected to be stable because of the large desorption barriers. The importance of nonbonded interactions was more noticeable as we moved from primary to tertiary alkyl radicals. Indeed, for the tert‐butyl radical, physisorption onto the (11,0) SWCNT is preferred rather than chemisorption. The bond dissociation energies determined for alkyl radicals and SWCNT follow the trend suggested by the consideration of radical stabilization energies. However, they are in disagreement with some degrees of functionalization observed in recent experiments. This discrepancy would stem from the fact that for some HiPco nanotubes, nonbonded interactions with alkyl radicals are stronger than covalent bonds. © 2012 Wiley Periodicals, Inc.