The adsorption of aniline on SWCNTs has been investigated using three different DFT methods, PW91LYP, the hybrid m-GGA MPWB1K, and the dispersion-corrected BP86-D functionals. The BSSE-corrected adsorption energies for top orientation of aniline to the nanotube surface are Eads = 9.7 kcal mol?1 and Eads = 1.4 kcal mol?1 with BP86-D/SVP and MPWB1K/6-311+G(d), respectively. Results validated that the adsorption energy of aniline depends on the diameter of the nanotube with a pronounced manner, especially for small diameters. The TDDFT calculations of UV/vis spectra predict two electronic transitions resulting from nanotube excitations in the visible spectra (>500 nm) and one imperceptible aniline → SWCNT excitation at ca. 1200 nm. Inclusion of solvent effects (MeOH) by explicit solvent molecules leads to a pronounced red shift of the weak longest wavelength aniline → nanotube transition, whereas the strong intratube excitations are only a little influenced. Fluorescence excitation spectra (Λem = 586 nm) of SWCNTs in aniline yield a broad structured absorption in the range of 22?000?18?000 cm?1, which is insensitive to the addition of methanol as cosolvent.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films