Experimental verification of field-enhanced molecular vibrational scattering at single infrared antennas

Abstract: Surface-enhanced infrared absorption (SEIRA) spectroscopy exploits the field enhancement near nanophotonic structures for highly sensitive characterization of (bio)molecules. The vibrational signature observed in SEIRA spectra is typically interpreted as field-enhanced molecular absorption. Here we study molecular vibrations in the near field of single antennas and show that the vibrational signature can be equally well explained by field-enhanced molecular scattering. Although the infrared scattering cross section of molecules is negligible compared to their absorption cross section, the interference between the molecular-scattered field and the incident field enhances the spectral signature caused by molecular vibrational scattering by 10 orders of magnitude, thus becoming as large as that of field-enhanced molecular absorption. We provide experimental evidence that field-enhanced molecular scattering can be measured, scales in intensity with the fourth power of the local field enhancement and fully explains the vibrational signature in SEIRA spectra in both magnitude and line shape. Our work may open new paths for developing highly sensitive SEIRA sensors that exploit the presented scattering concept.