Uncovering low-frequency vibrations in surface-enhanced Raman of organic molecules

Alexandra Boehmke Amoruso, Roberto A. Boto, Eoin Elliot, Bart Nijs, Ruben Esteban, Tamás Földes, Fernando Aguilar-Galindo, Edina Rosta, Javier Aizpurua () and Jeremy J. Baumberg ()
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Alexandra Boehmke Amoruso: University of Cambridge
Roberto A. Boto: Centro de Física de Materiales CFM-MPC (CSIC UPV/EHU)
Eoin Elliot: University of Cambridge
Bart Nijs: University of Cambridge
Ruben Esteban: Centro de Física de Materiales CFM-MPC (CSIC UPV/EHU)
Tamás Földes: University College London
Fernando Aguilar-Galindo: Donostia International Physics Center (DIPC)
Edina Rosta: University College London
Javier Aizpurua: Donostia International Physics Center (DIPC)
Jeremy J. Baumberg: University of Cambridge

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract Accessing the terahertz (THz) spectral domain through surface-enhanced Raman spectroscopy (SERS) is challenging and opens up the study of low-frequency molecular and electronic excitations. Compared to direct THz probing of heterogenous ensembles, the extreme plasmonic confinement of visible light to deep sub-wavelength scales allows the study of hundreds or even single molecules. We show that self-assembled molecular monolayers of a set of simple aromatic thiols confined inside single-particle plasmonic nanocavities can be distinguished by their low-wavenumber spectral peaks below 200 cm−1, after removal of a bosonic inelastic contribution and an exponential background from the spectrum. Developing environment-dependent density-functional-theory simulations of the metal-molecule configuration enables the assignment and classification of their THz vibrations as well as the identification of intermolecular coupling effects and of the influence of the gold surface configuration. Furthermore, we show dramatically narrower THz SERS spectra from individual molecules at picocavities, which indicates the possibility to study intrinsic vibrational properties beyond inhomogeneous broadening, further supporting the key role of local environment.

Date: 2024
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DOI: 10.1038/s41467-024-50823-x

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