Exohedral and endohedral adsorption of nitrogen on the sidewall of single-walled carbon nanotubes

Abstract

Different configurations of a single nitrogen atom adsorbed at different sites on the sidewall of single-walled carbon nanotubes (SWNT's) are studied through first-principles calculations. It is found that the outer surface of the tube wall is reactive to the nitrogen atom, and a nitrogen atom can be chemically adsorbed on it forming an exohedral complex with a binding energy of $\ensuremath{\sim}3.86\mathrm{eV}$ for a (5,5) SWNT. Although the inner surface of the tube wall is less reactive than the outer surface, a nitrogen atom can still be adsorbed on the inner wall of the (5,5) tube forming an endohedral complex with the binding energy on the order of $\ensuremath{\sim}1.78\mathrm{eV}.$ The local structure of the SWNT around the adsorption sites is substantially changed. From studying the binding energies of a nitrogen atom adsorbed on different armchair tubes $(n,n)$ with n ranging from 5 to 16, it is found that the binding energy for exohedral adsorption decreases significantly with increasing radius (or increasing $n)$ of the tube, while for endohedral adsorption the binding energy varies slightly. The influence of endohedral adsorption of a single nitrogen atom on the local density of states of a (5,5) SWNT is also discussed.