Abstract
Tip-enhanced near-field Raman scattering (TERS) spectroscopy using an apertureless metallic probe tip realizes nanoscale observation of molecular vibrations in practical use. The tip provides two enhancement effects; one is caused by an enhanced electric field because of the localized surface plasmon polariton excitations, and the other is generated as a result of a chemical interaction between samples and the tip. These effects are analogous to the electromagnetic mechanism and the charge transfer mechanism of surface enhanced Raman scattering (SERS), respectively. This chapter reports on TERS spectra of adenine, a DNA base, where the observed Raman bands exhibits similar frequency shifts to the conventional SERS. It is found that the vibrational frequencies of several Raman bands of the TERS unambiguous shift to the values of the corresponding bands in SERS. This chapter describes the experimental results of the TERS spectroscopy of a single nanocrystal of DNA-base adenine molecules using a silver-coated apertureless probe of an atomic force microscope. The chapter analyzes the detected TERS bands in comparison with the bands obtained in the conventional SERS spectrum by performing high-level density functional theory (DFT) calculations of the silver-adenine (1:1) complexes.
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