Molecular Tuning of Charge-Transfer Resonance in Plasmonic Nanocavities

Abstract

Interfacial charge-transfer processes play a critical role in plasmon-enhanced spectroscopy, yet the energetic conditions governing charge-transfer resonance within molecule-metal nanocavities remain poorly understood. Here, plasmonic nanoparticle-on-mirror junctions incorporating systematically engineered biphenylthiol derivatives monolayers were used to investigate how frontier orbital alignment influences chemical enhancement mechanisms. A molecular library spanning a broad range of electronically tuned acceptor states was examined using surface-enhanced Raman scattering (SERS), vibrational sum frequency generation (vSFG) spectroscopy, and density functional theory calculations. By combining different excitation wavelengths with controlled variation of substrate composition and molecular electronic structure, the energetic relationship between plasmon-enhanced charge transfer excitation and molecular orbital alignment was quantitatively evaluated. The results reveal that charge-transfer enhancement of Raman scattering is governed by a well-defined interfacial resonance condition dependent on substrate work function and excitation energy. We further probe a subset of molecular-metal systems by nanocavity-enhanced vSFG and identify the same resonance conditions as in SERS, consistent with expectations. These findings establish an experimentally accessible framework for probing and engineering charge-transfer processes in plasmonic molecular junctions and provide mechanistic insight relevant to molecular plasmonics, charge carrier photophysics, and nanoscale interfacial spectroscopy.