Density functional theory evidence for an electron hopping process in single-walled carbon nanotube-mediated redox reactions

The electron hopping mechanism in the single-walled carbon nanotube (SWCNT)-mediated redox reaction between anthraquinonyl (AQH2) and 4-arylhydroxyl amine (4AHA) groups is studied by density functional theory calculations. The (8, 0) SWCNT is used to mimic the real system of interest. It is found that electrons from the oxidized AQH2 group can be transferred to the oxidizing 4AHA group, at the other end of the nanotube, by a hopping process through the mediating SWCNT. Disparity of electron densities ascribable to non-localized electrons confirms this finding. The disparity, partial electron density difference, and Hirshfeld partial charges analyses show that the SWCNT can hold 87% of the extra electron density of the hypothetical negative intermediate produced from the oxidation of the AQH2 process. Chemical attachments of these two redox reagents to the SWCNT also cause new impurity states within the band gap, thereby giving more metallic characteristics to the system. These findings provide a detailed understanding of the electron hopping process and agree well with a previous experimental study.