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 StoneWales-defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and StoneWales-defective nanotubes. The reaction energy for per F2 addition is between 85 and 88 kcal?mol-1 more negative than that per H2 addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.982.52 to 0.801.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying-tube-shaped SWCNTs with multiple CD defects are substantially increased to 1.653.85 eV. Furthermore, analyses of thermodynamic stability and nucleus-independent chemical shifts (NICS) are performed to analyze the stability of these molecules.