This presentation focuses on the dynamic interactions between surface-capping ligands and plasmonic nanoparticle surfaces. The interfacial adsorption, desorption, and exchange behaviors of capping ligands on textured nanoparticle surfaces exhibit phenomenal site-to-site variations essentially dictated by the local surface curvatures and surface atomic coordinations, resulting in heterogeneous thermodynamic and kinetic profiles remarkably more sophisticated than those associated with ligand binding to atomically flat surfaces of planar substrates. We use surface-enhanced Raman scattering (SERS) as a plasmon-enhanced spectroscopic tool with unique time-resolving and molecular fingerprinting capabilities to quantitatively correlate the interfacial ligand dynamics with detailed molecular structures in real time under a diverse set of ligand adsorption, desorption, and exchange conditions at both equilibrium and non-equilibrium states. The time-resolved SERS measurements allow us to gain mechanistic insights into the effects of nanoscale surface curvature on the binding affinity, cooperativity, structural ordering, and the adsorption/desorption/exchange dynamics of 3 types of ligands, including aromatic thiols, isocyanides, and diazomium compounds on colloidal metallic nanoparticles. The insights gained from the SERS results provide an important knowledge framework for us to fully understand the interfacial chemistry and photochemistry of ligand molecules on locally curved nanoparticle surfaces.  <br/>

Ligand dynamics and chemistry on plasmonic nanoparticle surfaces: Insights from plasmon-enhanced spectroscopy

2019 Spring National Meeting

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