Correlated Polarization Dependences between Surface-Enhanced Resonant Raman Scattering and Plasmon Resonance Elastic Scattering Showing Spectral Uncorrelation to Each Other

J Phys Chem B. 2023 May 25;127(20):4666-4675. doi: 10.1021/acs.jpcb.3c01878. Epub 2023 May 16.

Abstract

We investigated the origin of the identical polarization angle dependence between surface-enhanced resonant Raman scattering (SERRS) and plasmon resonance elastic scattering (PRES) for two types of single silver nanoparticle aggregates. The first type (Type I), in which the SERRS spectral envelopes are similar to the PRES spectra, shows the identical polarization dependence between the SERRS and PRES. The second type (Type II), in which the SERRS envelopes largely deviate from the PRES spectra, also exhibits identical polarization dependence. Scanning electron microscopy observations indicated that the aggregates were dimers. This unintuitive result was examined by calculating the electromagnetic enhancement by changing the morphology of the dimers. The calculations revealed that the Type I dimer generates SERRS directly by superradiant plasmons. The Type II dimer generates SERRS indirectly via subradiant plasmons, which receive light energy from superradiant plasmons. This indirect SERRS process clarifies that the interaction between the superradiant and subradiant plasmons results in an identical polarization dependence between SERRS and PRES for Type II dimers.