The spectral evolution of the surface-enhanced Raman scattering (SERS) of 4-tert-butylbenzylmer-captan (4-tBBM) on gold nanoparticles assembly under laser irradiation is reported. The relative intensities of typical peaks in the spectrum of 4-tBBM gradually change with irradiation time. Comparison of the rate of spectral changes under several experimental conditions indicates that the surface plasmon resonance (SPR) induced heat in the gold nanoparticles assembly is the origin of the spectral evolution. During the process of self-assembly, 4-tBBM molecules do not form a compact ordered monolayer because of the spatial hindrance of the 4-tert-butyl end group. The heat induced by laser irradiation drives the 4-tBBM molecules to rearrange to a more stable orientation.
