Dataset supporting the paper "Single-molecule mid-infrared spectroscopy and detection through vibrationally assisted luminescence" to reproduce all main figures.

Fig. 1: a, Electronic and vibrational absorption spectra of an MB molecule in solution. Arrows indicate NIR and MIR tuning. Inset: supramolecular assembly of MB inside a cucurbit[7]uril (CB) host molecule. b, Energy diagram of the electronic and vibrational levels of the MB molecule, indicating that the NIR pump (red arrow) drives the electronic transition only in the presence of MIR (yellow arrow). c, Silver-coated microsphere constructed on a thin metal foil (MSoF) as well as the alternative gold nanoparticle-on-foil (NPoF) construct. d, Bright-field optical image of an individual MSoF construct. e, Fourier-transform infrared spectroscopy of an individual MSoF cavity assembled with a monolayer of MB–CB (solid grey line), compared to simulated extinction of the NPoF cavity (dotted grey line). f, Simulated near field of the MSoF cavity at λMIR = 10 µm.

Fig. 2: a, MIR detection set-up with the pump illuminating an individual MSoF cavity. Incident light is modulated (dashed lines) by an acousto-optic modulator for the pump and a QCL laser for the MIR. b, Stokes and anti-Stokes emission from the pump, with (orange) and without (grey) MIR light of average power 0.5 µW µm−2, averaged over ten scans on a single MSoF cavity. c, Percentage difference in emitted signals transduced by MIR in b. PL, photoluminescence. d, Modulation of aS-PL intensity switching the MIR beam on and off. e, MIR transduced signal when tuning the pump from λpump = 750 nm (top) to 785 nm (bottom) in 5-nm steps (arrows indicate λpump). Direct visible pumping at 633 nm is shown for comparison (top, grey curve). f, Spectrally integrated transduced signal from e versus λpump for three different MSoF cavities, compared with absorption spectra of MB molecules in solution, rigidly shifted by ωMIR (solid line).

Fig. 3: a,b, aS-PL intensity when tuning the MIR photon energy (orange points) for MB (a) and RhB (b) molecules assembled in MSoF cavities, compared to FTIR measurements in solution (grey). c,d, Power-dependent integrated aS-PL intensity for increasing MIR (c) and pump (d) average powers, using MSoF (orange) and NPoF (yellow). Solid lines show power-law fits with an exponent of one. The detection noise floor is 100 cts s−1.

Fig. 4: a,b, Repeated aS-PL and SERRS spectra for a single MSoF cavity with a pump of 0.5 mW μm−2 at 750 nm. The top arrow shows MIR tuning. The transient picocavity event starts at τP. c, Corresponding variations in the aS-PL and SERRS intensities exhibit strong correlation. The picocavity regime is highlighted in black dashed boxes. d,e, Similar aS-PL and SERRS intensity tracks for another two different MSoF cavities with pump of 0.7 mW μm−2 pump. Spectral maps are shown in Supplementary Fig. 12.