Probing the chemical functionalization of single-walled carbon nanotubes with multiple carbon ad-dimer defects

Drying-tube-shaped single-walled carbon nanotubes (SWCNTs) with multiple carbon ad-dimer (CD) defects are obtained from armchair (n,n,m) SWCNTs (n=4, 5, 6, 7, 8; m=7, 13). According to the isolated-pentagon rule (IPR) the drying-tube-shaped SWCNTs are unstable non-IPR species, and their hydrogenated, fluorinated, and chlorinated derivatives are investigated. Interestingly, chemisorptions of hydrogen, fluorine, and chlorine atoms on the drying tube-shaped SWCNTs are exothermic processes. Compared to the reaction energies for binding of H, F, and Cl atoms to perfect and Stone-Wales-defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and Stone-Wales-defective nanotubes. The reaction energy for per F(2) addition is between 85 and 88 kcal mol(-1) more negative than that per H(2) addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.98-2.52 to 0.80-1.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying-tube-shaped SWCNTs with multiple CD defects are substantially increased to 1.65-3.85 eV. Furthermore, analyses of thermodynamic stability and nucleus-independent chemical shifts (NICS) are performed to analyze the stability of these molecules.