Optical absorption and energy loss spectroscopy of single-walled carbon nanotubes

Abstract

The recent development of efficient chirality sorting techniques has opened the way to the use of single-walled carbon nanotubes (SWCNTs) in a plethora of nanoelectronic, photovoltaic, and optoelectronic applications. However, to understand the excitation processes undergone by SWCNTs, it is necessary to have highly efficient and accurate computational methods to describe their optical and electronic properties, methods which have until now been unavailable. Here we employ linear combinations of atomic orbitals (LCAOs) to represent the Kohn-Sham (KS) wavefunctions and perform highly efficient time dependent density functional theory (TDDFT) calculations in the frequency domain using our LCAO-TDDFT-$k$-$\omega$ code to model the optical absorbance and energy loss spectra and spatial distribution of the exciton charge densities in SWCNTs. By applying the GLLB-SC derivative discontinuity correction to the KS eigenenergies, we reproduce the measured $E_{11}$ and $E_{22}$ transitions within $\sigma \lesssim 70$ meV and the optical absorbance and electron energy loss spectra semi-quantitatively for a set of fifteen semiconducting and four metallic chirality sorted SWCNTs. Furthermore, our calculated electron hole density difference $\Delta \rho(\textbf{r}, \omega)$ resolves the spatial distribution of the measured excitations in SWCNTs. These results open the path towards the computational design of optimized SWCNT nanoelectronic, photovoltaic, and optoelectronic devices $\textit{in silico}$.