Intermolecular Interaction between Single-Walled Carbon Nanotubes and Encapsulated Molecules Studied by Polarization...

In the present study, we investigated the intermolecular interactions between single-walled carbon nanotubes (SWCNTs) and encapsulated molecules by polarization resonance Raman microscopy. C₇₀ encapsulated in SWCNTs is investigated under incident laser polarization parallel and perpendicular to the tube axis. We employed two excitation laser wavelengths 442 and 532 nm, which are in resonance with different electronic states of C₇₀. Under 532 nm excitation, no distinct polarization dependence is found in the Raman spectral pattern, while under 442 nm excitation, a peak not previously seen for this excitation wavelength was clearly observed for parallel excitation. This result can be explained by the modulation of the resonance Raman process via a charge transfer contribution between C₇₀ and the SWCNTs, which is sensitive to the incident polarization as well as the excitation wavelength. The intensity of the local electronic field inside a SWCNT is higher for the parallel excitation than the perpendicular excitation when the nanotubes are in a bundle. The results can be explained by field localization effects at the nanotube walls, qualitatively supported by finite-difference time-domain simulations.