In situ Raman spectroscopic measurements with 785 nm excitation were carried out in aqueous solutions containing bipyridine derivatives. Intense Raman signals were observed when the Ag dimer structure was optimized. The SERS activity was dependent upon on the structure of the Ag dimer with a distinct gap distance, suggesting that the intense SERS originates from the gap part of the dimer. Characteristic time-dependent spectral changes were observed. Not only a spectrum which was the superposition of two bipyridine spectra but also spectra which can be assigned to one of the bipyridine derivatives were frequently observed. Observation using solutions with different concentrations proved that the spectra originated from very small numbers of molecules at the active SERS site of the dimer.

The in situ observation of geometrical and electronic structural dynamics of a single molecule junction is critically important in order to further progress in molecular electronics. Observations of single molecular junctions are difficult, however, because of sensitivity limits. Here, we report surface-enhanced Raman scattering (SERS) of a single 4,4'-bipyridine molecule under conditions of in situ current flow in a nanogap, by using nano-fabricated, mechanically controllable break junction (MCBJ) electrodes. When adsorbed at room temperature on metal nanoelectrodes in solution to form a single molecule junction, statistical analysis showed that nontotally symmetric b(1) and b(2) modes of 4,4'-bipyridine were strongly enhanced relative to observations of the same modes in solid or aqueous solutions. Significant changes in SERS intensity, energy (wavenumber), and selectivity of Raman vibrational bands that are coincident with current fluctuations provide information on distinct states of electronic and geometrical structure of the single molecule junction, even under large thermal fluctuations occurring at room temperature. We observed the dynamics of 4,4'-bipyridine motion between vertical and tilting configurations in the Au nanogap via b(1) and b(2) mode switching. A slight increase in the tilting angle of the molecule was also observed by noting the increase in the energies of Raman modes and the decrease in conductance of the molecular junction.

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