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 nanotube. Surprisingly, the kinetic barrier follows an empirical
Br{\o}nsted-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.Comment: 10 pages, Supporting information, The Journal of Physical Chemistry C
(2015
