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We present the experimentally obtained single-molecule (SM) surface-enhancedRaman scattering (SERS) spectrum of 4-aminibenzenethiol (4-ABT), also known aspara-aminothiophenol (PATP). Measured at a 4-ABT concentration of 8 * 10^-10 M,the spectra show Raman forbidden modes. The SM-SERS spectrum of 4-ABT obtainedusing a non-resonant visible laser is different from the previously reportedSERS spectra of 4-ABT, and could not be reconstructed using quantum mechanicalcalculations. Careful classical assignments (not based on quantum-mechanicalcalculations) are reported, and indicate that differences in the reportedspectra of 4-ABT are mainly due to the appearance of Raman forbidden bands. Thepresence of Raman forbidden bands can be explained by the charge-transfer (CT)effect of 4-ABT adsorbed on the silver nanostructures, indicating a breakdownof Raman selection rules at the SERS hotspot.

Single-Molecule Surface-Enhanced Raman Scattering Spectrum of Non-Resonant Aromatic Amine Showing Raman Forbidden Bands