Surface enhanced infrared absorption mechanism and modification of the plasmonic response

Abstract

Surface Enhanced Infrared Absorption (SEIRA) is an experimental method where trace amount of a compound can be detected with high sensibility. This high detection sensibility is the result of the interaction of the molecules with a localized plasmon, usually from a metallic nano-particle. In this study we numerically investigate by discrete dipole approximation the origin of the Fano-like response of the system, including the induced transparency when the plasmon resonance and the molecular vibrational mode coincide. The detailed analysis of the localization of the absorption show that the modification of the absorption cross-section when the molecule is present comes from a change of the plasmonic resonance, not from the direct molecular response which is negligible. This sheds a new light on the SEIRA mechanism. In particular, it demonstrates that the sensibility is associated with the influence of the molecule on the plasmon resonance rather than with the local field enhancement itself.

Surface-Enhanced Infrared Absorption Spectroscopy by Resonant Vibrational Coupling with Plasmonic Metal Oxide Nanocrystals

“…Small gold and silver NCs exhibit LSPR at visible light frequencies. To shift their LSPR to the mid-IR for resonance with molecular vibrations, significantly larger NCs such as nanorods , or nanoshells are necessary, which can be challenging to synthesize with uniform morphologies and to assemble in regular superstructures. IR resonances can also arise in multilayer films of larger gold NCs due to plasmon-polariton modes. , However, these strategies all lead to large mode volumes, which reduce achievable electric field intensities, and to low spatial densities of hot spots, disfavoring strong enhancement of vibrational signals detected in the far field.…”

“…Small gold and silver NCs exhibit LSPR at visible light frequencies. To shift their LSPR to the mid-IR for resonance with molecular vibrations, significantly larger NCs such as nanorods 23,29 or nanoshells 30 are necessary, which can be challenging to synthesize with uniform morphologies and to assemble in regular superstructures. IR resonances can also arise in multilayer films of larger gold NCs due to plasmonpolariton modes.…”