Effect of Curvature on Carbon Chemical Shielding in Extended Carbon Systems.

Abstract

The effect of curvature on the chemical shielding of carbons in curved polycyclic aromatic hydrocarbons has been systematically studied by examining structures analogous to the circumcoronene molecule with different degrees of curvature. We attempt to eliminate effects from Knight shifts in carbon nanotubes, differing ring currents from five-membered rings, and edge effects in finite nanotube models in order to separate out the change in shielding that is due to curvature alone. Using curved structures derived from geometry-optimized structures of carbon nanotubes, we calculate the carbon chemical shielding tensor for carbons in the central aromatic ring as well as the Nucleus Independent Chemical Shift (NICS) on the convex and concave side of each structure. All three tensor components become less shielded with increasing curvature of the system, with the σ33 component radial to the curve experiencing the greatest change. The NICS values are influenced by both the decrease in aromaticity as the structure is curved as well as geometric effects that bring the outside rings closer to the central aromatic ring.