While the past decade has seen the almost explosive emergence of the field of plasmonics, much credit is due the initial researchers in this field who established surface plasmons of metallic nanostructures as playing a key role in certain chemical and photophysical processes. In the area of surface enhanced Raman spectroscopy, the importance of closely adjacent, coupled metallic nanoparticles was the critical insight instrumental to the idea that coupled    plasmons of   adjacent metallic nanoparticles mix and hybridize in analogy with molecular orbital theory. Coupled metallic nanostructures can now be exploited in the controlled enhancement of other spectroscopic modalities, such as surface-enhanced infrared absorption (SEIRA) spectroscopy, where individual nanoantennas with detection sensitivities at zeptomolar concentrations- using conventional IR spectroscopic sources- can be tuned to the vibrational frequencies of specific chemical moieties. In SEIRA, the �lightning rod effect� arising from the nanoscale gap between antenna arms is responsible for the large enhancements that can be observed with these structures. Important nonlinear analogs of SERS, such as Four-wave mixing (FWM) and surface-enhanced CARS (SECARS), can be enhanced in a controlled and systematic manner by utilizing multiparticle plasmonic clusters designed with two specific, frequency-offset �bright� or �dark� (Fano) resonances. Other plasmon-derived chemical effects, such as the emission of hot electrons from metallic nanoparticles due to plasmon decay, hold great promise in the development of photocatalysts for chemical reactions and other photophysical processes.

Plasmon-enabled nanoparticle-based chemistry and spectroscopies

246th National Meeting (2013)

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