Absorption spectroscopy

Abstract: Fluorescence has been observed directly across the band gap of semiconducting carbon nanotubes. We obtained individual nanotubes, each encased in a cylindrical micelle, by ultrasonically agitating an aqueous dispersion of raw single-walled carbon nanotubes in sodium dodecyl sulfate and then centrifuging to remove tube bundles, ropes, and residual catalyst. Aggregation of nanotubes into bundles otherwise quenches the fluorescence through interactions with metallic tubes and substantially broadens the absorption spectra. At pH less than 5, the absorption and emission spectra of individual nanotubes show evidence of band gap-selective protonation of the side walls of the tube. This protonation is readily reversed by treatment with base or ultraviolet light.

Abstract: The use of optical measurements to monitor electrochemical changes on the surface of nanosized metal particles is discussed within the Drude model. The absorption spectrum of a metal sol in water is shown to be strongly affected by cathodic or anodic polarization, chemisorption, metal adatom deposition, and alloying. Anion adsorption leads to strong damping of the free electron absorption. Cathodic polarization leads to anion desorption. Underpotential deposition (upd) of electropositive metal layers results in dramatic blue-shifts of the surface plasmon band of the substrate. The deposition of just 0.1 monolayer can be readily detected by eye. In some cases alloying occurs spontaneously during upd. Alloy formation can be ascertained from the optical absorption spectrum in the case of gold deposition onto silver sols. The underpotential deposition of silver adatoms onto palladium leads to the formation of a homogeneous silver shell, but the mean free path is less than predicted, due to lattice strain in t...

Abstract: Spectrofluorimetric measurements on single-walled carbon nanotubes (SWNTs) isolated in aqueous surfactant suspensions have revealed distinct electronic absorption and emission transitions for more than 30 different semiconducting nanotube species. By combining these fluorimetric results with resonance Raman data, each optical transition has been mapped to a specific (n,m) nanotube structure. Optical spectroscopy can thereby be used to rapidly determine the detailed composition of bulk SWNT samples, providing distributions in both tube diameter and chiral angle. The measured transition frequencies differ substantially from simple theoretical predictions. These deviations may reflect combinations of trigonal warping and excitonic effects.