Resonant coupling between plasmonic nanoantennas and molecular vibrational ex-citations is employed to amplify the weak overtone transitions that reside in the nearinfrared. We explore for the first time the differential extinction of forbidden molecular overtone transitions coupled to the localized surface plasmons. We show that a nontrivial interplay between the molecular absorption enhancement and suppression of plasmonic absorption in a coupled system gives rise to orders of magnitude enhancement of the probe molecule differential extinction. Our results pave a road toward a new class of surface enhanced near-infrared absorption-based sensors.
Molecular overtones stretching modes that occupy the near-infrared (NIR) are weak compared to the fundamental vibrations. Here we report on the enhancement of absorption by molecular vibrations overtones via electromagnetic field enhancement of plasmonic nanoparallelepipeds comprising a square lattice. We explore numerically, using finite element method (FEM), gold metasurfaces on a transparent dielectric substrate covered by weakly absorbing analyte supporting N-H and C-H overtone absorption bands around 1.5 μ m and around 1.67 μ m, respectively. We found that the absorption enhancement in N-H overtone transition can be increased up to the factor of 22.5 due to the combination of localized surface plasmon resonance in prolonged nanoparticles and lattice Rayleigh anomaly. Our approach may be extended for sensitive identification of other functional group overtone transitions in the near-infrared spectral range.
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