Scaling Law of Quantum Confinement in Single-Walled Carbon Nanotubes (2410.21672v1)

Abstract: Quantum confinement significantly influences the excited states of sub-10 nm single-walled carbon nanotubes (SWCNTs), crucial for advancements in transistor technology and the development of novel opto-electronic materials such as fluorescent ultrashort nanotubes (FUNs). However, the length dependence of this effect in ultrashort SWCNTs is not yet fully understood in the context of the SWCNT exciton states. Here, we conduct excited state calculations using time-dependent density functional theory (TD-DFT) on geometry-optimized models of ultrashort SWCNTs and FUNs, which consist of ultrashort SWCNTs with $sp^3$ defects. Our results reveal a length-dependent scaling law of the $E_{11}$ exciton energy that can be understood through a geometric, dimensional argument, and which departs from the length scaling of a 1D particle-in-a-box. We find that this scaling law applies to ultrashort (6,5) and (6,6) SWCNTs, as well as models of (6,5) FUNs. In contrast, the defect-induced $E_{sp^3}$ transition, which is redshifted from the $E_{11}$ optical gap transition, shows little dependence on the nanotube length, even in the shortest possible SWCNTs. We attribute this relative lack of length dependence to orbital localization around the quantum defect that is installed near the SWCNT edge. Our results illustrate the complex interplay of defects and quantum confinement effects in ultrashort SWCNTs and provide a foundation for further explorations of these nanoscale phenomena.