Colocalized Raman and IR Spectroscopies via Vibrational-Encoded Fluorescence for Comprehensive Vibrational Analysis

Vibrational spectroscopy, including Raman scattering and infrared (IR) absorption, provides essential molecular fingerprint information, facilitating diverse applications, such as interfacial sensing, chemical analysis, and biomedical diagnostics. The complementary selection rules of Raman and IR spectroscopies offer distinct, yet mutually reinforcing, insights into molecular structure and dynamics. However, in dynamic or complex chemical environments, either technique alone is not capable of providing a complete and nuanced picture of molecular vibrations. Simultaneous detection of complementary vibrational modes within the same molecular group remains challenging due to wavelength discrepancies and sensitivity mismatches between Raman and IR spectroscopies. In this work, to address the gap between these spectroscopies, we developed an integrated approach based on vibrational-encoded fluorescence (VEF), in which the complementary vibrational information is respectively encoded into the different parts of fluorescence radiation: Stokes fluorescence carrying Raman information and anti-Stokes fluorescence reflecting IR information. This method employs a dual-resonant microsphere-on-mirror plasmonic structure to bridge the waveband gap, enabling the simultaneous detection of complete vibrational modes in the visible spectrum with ultrahigh sensitivity down to ∼100 molecules. Hyperspectral colocalization imaging demonstrates spatial correlations between the complementary vibrations. By careful calibration, the detection efficiency is improved by 8 orders of magnitude compared to unenhanced IR spectroscopy. This approach creates new opportunities for the precise identification of molecular vibrational information in complex chemical environments.