The sp3 Defect Decreases Charge Carrier Lifetime in (8,3) Single-Walled Carbon Nanotubes

J Phys Chem Lett. 2023 Nov 16;14(45):10242-10248. doi: 10.1021/acs.jpclett.3c02923. Epub 2023 Nov 8.

Abstract

A recent experimental approach introduces sp3 defects into single-walled carbon nanotubes (SWNTs) through controlled functionalization with guanine, resulting in a decrease in charge carrier lifetime. However, the physical mechanism behind this phenomenon remains unclear. We employ nonadiabatic molecular dynamics to systematically model the nonradiative recombination process of electron-hole pairs in SWNTs with sp3 defects generated by a guanine molecule. We demonstrate that the introduction of sp3 defects creates an overlapping channel between the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO), significantly enhancing the nonadiabatic (NA) coupling and leading to a 4.7-fold acceleration in charge carrier recombination compared to defect-free SWNTs. The charge carrier recombination slows significantly at a lower temperature (50 K) due to the weakening of the NA coupling. Our results rationalize the accelerated recombination of charge carriers in SWNTs with sp3 defects in experiments and contribute to a deeper understanding of the carrier dynamics in SWNTs.