Organothiol (R-SH) (OT) adsorption onto silver nanoparticles (AgNPs) in water was studied for a series of aromatic OTs including p-methylbenzenethiol (p-MBT), p-benzenedithiol (p-BDT), and 2-mercaptobenzimidazole (2-MBI). Unlike the common view that OT forms monolayer adsorption on AgNPs, we found that these aromatic OTs continuously reacted with AgNPs through formation of RS–Ag complexes until complete OT or AgNP consumption occurred. The RS–Ag complex can remain on the AgNP surface, converting the AgNPs into core–shell structures. The OT adsorption onto AgNPs occurs predominately through reaction with silver oxide present on the AgNP surfaces before the OT addition or formed from environmental oxygen in the presence of OT. The RS–H protons are completely released when both p-MBT and 2-MBI reacted with AgNP, Ag2O, and AgNO3. However, a substantial fraction of S–H bonds remained intact when p-BDT, the only dithiol used in this work, is adsorbed on AgNPs or reacted independently with Ag2O and AgNO3. The new insights from this work should be important for understanding OT interaction with AgNPs in water and the SERS spectra of the OT adsorbed onto AgNPs.

Using a two-layer metal nanoparticle dimer array, we numerically show that the array can act as an efficient circular polarizer. Linearly polarized incident light can be completely split into right and left circularly polarized light. The simulation results show that the efficiency of the polarizer depends on the size of the nanoparticles, the gap distance between the two particles in the dimers, the distance between the two layers, and the relative orientation between the dimer axes in the two layers. The periodic distance between two neighboring dimers in one layer is also a crucial factor affecting the splitting efficiency. The simulation results demonstrate a simple route of using plasmonic nanomaterials for designing efficient circular polarizers.

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