Noncovalent functionalization of carbon nanotubes and graphene with tetraphenylporphyrins: Stability and optical properties from ab-initio calculations

Abstract: The stability, electronic and optical properties of single-walled carbon nanotubes (CNTs) and graphene noncovalently functionalized with free-base tetraphenylporphyrin (TPP) molecules is addressed by density functional theory calculations, including corrections to dispersive interactions. We study the TPP physisorption on 42 CNT species, particularly those with chiral indices ($n$,$m$), where $5 \leq n \leq 12$ and $0\leq m\leq n$. Our results show a quite strong $\pi$-$\pi$ interaction between TPP and the CNT surface, with binding energies ranging from 1.1 to 1.8 eV, where higher energies can be associated with increasing CNT diameters. We also find that the TPP optical absorptions would not be affected by the CNT diameter or chirality. Results for the TPP physisorption on graphene show a remarkable stability with binding energy of 3.2 eV, inducing a small redshift on the $\pi$-stacked TPP absorption bands. The strong graphene-TPP interaction also induces a charge transfer from TPP to graphene, indicating a $n$-type doping mechanism without compromising the graphene structure.