Upon optical excitation, certain plasmonic nanoparticle aggregates generate localized electric fields on the order of 100 times more intense than those associated with the incident radiation. These strong fields support surface enhanced spectroscopies such as SERS that are sensitive down to the single-molecule limit. Though much work has been done to characterize the fields surrounding plasmonic nanoparticles, little is known about how the electronic structure of a molecule changes when coupled strongly with such an aggregate. We have implemented a many-body Green's function approach to rigorously account for the interaction between a classically modeled metal nanoaggregate and a quantum mechanical molecule from first-principles. In the strong coupling regime, the energies of certain molecular excited states change drastically. In order to demonstrate the spectral and spatial dependence of our results, we map Fermi's golden rule in the region surrounding a plasmonic nanoparticle aggregate at several excitation frequencies.

Computing Fermi's golden rule in the presence of plasmonic nanoparticle aggregates

243rd National Meeting (2012)

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