4-Mercaptopyridine adsorbed on pure palladium island films: A combined SERS and DFT investigation

Surface-enhanced Raman scattering (SERS) can provide vibrational information with molecular specificity and potential single-molecule sensitivity. SERS studies on pure transition metals, however, remain challenging due to the weak SERS activity of transition metals compared to coinage metals. Here we fabricated alumina-supported Pd island films by depositing laser-ablated Pd colloids onto an Al substrate. Robust SERS signal employing 4-mercaptopyridine (4-Mpy) as a probe was registered from the as-prepared films. The adsorption information of 4-Mpy molecules such as orientation and coordinating site was discussed in detail based on SERS data. It was inferred that 4-Mpy adsorbs via its sulfur atom to Pd surface with a tilted binding configuration. The Raman wavenumber and intensity of an adsorption model including one 4-Mpy and Pd atom were computed using density functional theory (DFT) at the Beck’s three-parameter Lee–Yang–Parr (B3LYP) level with the LANL2DZ basis set. The simulated Raman spectrum was in good agreement with the experimental one except for the relative intensity. The current investigation could be helpful to gain a comprehensive understanding of SERS.