Adsorption of lanthanide double-decker phthalocyanines on single-walled carbon nanotubes: structural changes and electronic properties as studied by density functional theory

CONTEXT: Molecular modeling of carbon nanotubes and lanthanide double-decker phthalocyanines hybrids is challenging due to the presence of 4f-electrons. In this paper, we analyzed the trends in structural changes and electronic properties when a lanthanide (La, Gd, and Lu) bisphthalocyanine molecule is adsorbed on the surface of two single-walled carbon nanotubes (SWCNTs) models: armchair and zigzag. The density functional theory (DFT) computations showed that the height of bisphthalocyanines complexes (LnPc(2)) when adsorbed on a nanotube (LnPc(2)+SWCNT) is the structural feature which is most affected by the nanotube model. The formation energy of the LnPc(2)+SWCNT hybrid depends on the metal atom and the nanotube chirality. LaPc(2) and LuPc(2) bind stronger to the zigzag nanotube, while for GdPc(2), bonding to the armchair nanotube is the stronger one. The HOMO-LUMO gap energy (Egap) shows a correlation between the nature of lanthanide and the nanotube chirality. In the case of adsorption on armchair nanotube, E(gap) tends to match the gap of isolated LnPc(2), whereas for adsorption on the zigzag nanotube, it is closer to the value for the isolated nanotube model. The spin density is localized on the phthalocyanines ligands (plus on Gd in the case of GdPc(2)), when the bisphthalocyanine is adsorbed on the surface of the armchair nanotube. For bonding to zigzag nanotube (ZNT), it extends over both components, except for LaPc(2)+ZNT, where spin density is found on the nanotube only. METHOD: All DFT calculations were carried out using the DMol(3) module of Material Studio 8.0 software package from Accelrys Inc. The computational technique chosen was the general gradient approximation functional PBE in combination with a long-range dispersion correction developed by Grimme (PBE-D2), the double numerical basis set DN, and the DFT semi-core pseudopotentials. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s00894-023-05557-w.