Kinetics of Topological Stone–Wales Defect Formation in Single-Walled Carbon Nanotubes

Abstract

Topological Stone–Wales defect in carbon nanotubes plays a central role in plastic deformation, chemical functionalization, and superstructure formation. Here, we systematically investigate the formation kinetics of such defects within density functional approach coupled with the transition state theory. We find that both the formation and activation energies depend critically on the nanotube chairality, diameter, and defect orientation. The microscopic origin of the observed dependence is explained with curvature-induced rehybridization in nanotubes. Surprisingly, the kinetic barrier follows an empirical Brønsted–Evans–Polanyi-type correlation with the corresponding formation energy and can be understood in terms of overlap between energy-coordinate parabolas representing the structures with and without the defect. Further, we propose a possible route to substantially decrease the kinetic activation barrier. Such accelerated rates of defect formation are desirable in many novel electronic, mechanical, and chemical applications and also facilitate the formation of three-dimensional nanotube superstructures.