SERS and DFT study of crystal violet

Six silver colloids were prepared by the reduction of silver nitrate with different amounts of sodium citrate. The obtained silver colloids were characterised by UV–vis spectroscopy, transmission electron microscopy and zeta potential measurements. The surface-enhanced Raman scattering (SERS) activities of these silver colloids were investigated using crystal violet (CV) as a SERS probe. Based on density functional theory (DFT) calculations at the level of B3LYP, the Raman spectra and the optimised geometry of CV were analysed. The results show that the sodium citrate content strongly influences the sizes, zeta potentials and SERS activities of the silver colloids. As the sodium citrate content increases in the preparation of silver colloids, the mean diameters of the silver nanoparticles decrease. The most intense SERS of CV on the silver colloids is obtained when 3 mL of 1% sodium citrate is used. CV has D3 point group symmetry, and the Raman vibrational modes belong to A1 or E irreducible representations. The non-totally symmetric vibrational modes E are selectively enhanced in the SERS of CV through a Herzberg–Teller vibronic coupling mechanism, indicating a considerable charge transfer between CV and the silver nanoparticles.

► Six silver colloids were prepared by the reduction of AgNO3 with citrate. ► Six silver colloids have different SERS activities using CV as a probe. ► SERS of CV were assigned based on DFT calculation at the level of B3LYP. ► Non-totally symmetric vibrations are selectively enhanced in SERS of CV. ► The charge transfer between CV and silver contributes to SERS of CV.