Theoretical Study on Non-Linear Optics Properties of Polycyclic Aromatic Hydrocarbons and the Effect of Their Intercalation with Carbon Nanotubes

Results of a theoretical study devoted to comparing NLO (non-linear optics) responses of derivatives of tetracene, isochrysene, and pyrene are reported. The static hyperpolarizability β, the dipole moment μ, the HOMO and LUMO orbitals, and their energy gap were calculated using the CAM-B3LYP density functional combined with the cc-pVDZ basis set. The para-disubstituted NO2-tetracene-N(CH3)2 has the highest NLO response, which is related to a large intramolecular charge transfer. Adding vinyl groups to the para-disubstituted NO2-tetracene-N(CH3)2 results in an increase in the NLO responses. We further investigated the effect of the intercalation of various push–pull molecules inside an armchair single-walled carbon nanotube. The intercalation leads to increased NLO responses, something that depends critically on the position of the guest molecule and/or on functionalization of the nanotube by donor and attractor groups.