Investigation of particle shape and size effects in SERS using T-matrix calculations
Literature Information
Rufus Boyack, Eric C. Le Ru
The influence of particle size and shape effects on average and punctual surface-enhanced Raman scattering (SERS) enhancement factors (EFs) is investigated using exact T-matrix electrodynamic calculations of silver and gold spheroids over a large parameter space. This study extends the conventional treatment of these effects within the frameworks of the electrostatics approximation, its generalizations, or Mie theory for spheres. It confirms the qualitative features of these approaches, but provides in addition quantitative predictions of SERS EFs in the case of large non-spherical particles, where the lightning-rod effect (shape effect) and radiation damping (size effect) operate simultaneously. Finally, the localization effect at large SERS EF (hot-spots) is shown to be dictated only by shape, not size, in the case of metallic spheroids at the dipolar localized surface plasmon resonance.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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