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The optical probe of a scanning near-field optical microscope is shown to act as a point source of surface plasmon (SP) polaritons on gold and silver films. Plasmon excitation manifests itself by emission of light in the direction of the SP resonance angle, originating from an area with the shape of a dipole radiation pattern whose extension is given by the SP decay length. Interaction with selected, individual surface inhomogeneities gives rise to characteristic modifications of the emitted radiation, which provide detailed information about SP scattering, reflection, and interference phenomena. [S0031-9007(96)01079-4]

The tip-enhanced near-field Raman (TERS) bands of Rhodamine 6G (R6G), that we reported earlier [Chem. Phys. Lett. 2001, 335, 369.], are assigned on the basis of density-functional theory (DFT) calculations at the 6-311++G(d,p) level. The Raman and infrared intensities as well as frequencies of the vibrational modes are used for band assignments. These vibrational modes, in combination with characterization of resonant electronic transitions using time-dependent DFT calculations, predict spectral changes in resonant Raman and surface-enhanced resonant Raman scatterings of R6G. Moreover, the TERS spectra of R6G are analyzed in detail, where interactions between the tip and R6G molecules and their enhancement mechanisms are discussed. Finally, we propose a novel Raman spectroscopy technique capable of detecting molecular vibrations at sub-nanometer scale.

Near-field optical (NFO) microscopes with an auxiliary gap width regulation (shear force, tunneling) may produce images that represent the path of the probe rather than optical properties of the sample. Experimental and theoretical evidence leads us to the conclusion that many NFO results reported in the past might have been affected or even dominated by the resulting artifact. The specifications derived from such results for the different types of NFO microscopes used therefore warrant reexamination. We show that the resolving power of aperture NFO microscopes, 30–50 nm, is of genuine NFO origin but can be heavily obscured by the artifact.

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An electric field enhanced by a metallic nanoprobe has locally induced coherent anti-Stokes Raman scattering (CARS) of adenine molecules in a nanometric DNA network structure. Owing to the third-order nonlinearity, the excitation of the CARS polarization is extremely confined to the end of the tip apex, resulting in a spatial resolution far beyond the diffraction limit of light. Our tip-enhanced CARS microscope visualized the DNA network structure at a specific vibrational frequency (approximately 1337 cm(-1)) corresponding to the ring-breathing mode of diazole of adenine molecules.

We demonstrate dynamic imaging of molecular distribution in unstained living cells using Raman scattering. By combining slit-scanning detection and optimizing the excitation wavelength, we imaged the dynamic molecular distributions of cytochrome c, protein beta sheets, and lipids in unstained HeLa cells with a temporal resolution of 3 minutes. We found that 532-nm excitation can be used to generate strong Raman scattering signals and to suppress autofluorescence that typically obscures Raman signals. With this technique, we reveal time-resolved distributions of cytochrome c and other biomolecules in living cells in the process of cytokinesis without the need for fluorescent labels or markers.