Plasmon-Driven Chemistry as Revealed by Ultrafast SERS, Single Molecule SERS, and Electrochemical TERS

The current proposal aims to expand the fundamental understanding and advanced application of plasmonically enhanced spectroscopic methods and plasmon-driven chemistry. Three parallel yet synergistic goals are set forth: 1) Fundamental study of chemical enhancement contribution in order to generalize single molecule surface enhanced Raman spectroscopy (SMSERS) to non-resonant and/or small molecules. 2) Capitalizing on the newly developed surface-enhanced femtosecond stimulated Raman spectroscopy (SE-FSRS), and using it to interrogate the mechanism of plasmon-driven chemistry across multiple time scales. 3) Developing electrochemical tip-enhanced Raman spectroscopy (EC-TERS) and using it to study of heterogeneous electron transfer reactions down to the single site level with spatial resolution and chemical specificity. Leveraging the successful track record of developing novel spectroscopic methods, the Van Duyne group is uniquely positioned to push the limits in achieving surface-enhanced Raman excitation spectroscopy down to single molecule level, multi time-scale time-resolved SE-SRS spectroscopies, and multi-wavelength EC-TER spectroscopy and microscopy.