Surface enhanced infrared absorption mechanism and modification of the plasmonic response

Colleu, Tanguy [Solid State Laboratory (LPS), Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles 61, 5000 Namur, Belgium] Fekete, Adam [UCL] Gonze, Xavier [UCL] Cloots, Alexandre [UCL] Liégeois, Vincent [Theoretical Chemistry Laboratory (LCT), Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles 61, 5000 Namur, Belgium] Rignanese, Gian-Marco [UCL] Henrard, Luc [Solid State Laboratory (LPS), Namur Institute of Structured Matter (NISM), University of Namur, Rue de Bruxelles 61, 5000 Namur, Belgium]

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 nanoparticle. 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 shows 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.