Model-free Reconstruction of Molecular Energy Levels by Broadband Kilohertz-accurate Cavity-enhanced Spectroscopy
Assigning the lines of high-resolution molecular spectra to quantum states requires a Hamiltonian model and substantial expert intervention, so the spectra of larger molecules accumulate vast numbers of unassigned lines. Here we show that molecular energy levels can instead be reconstructed directly from the raw, unassigned transition frequencies, using graph theory alone with no model and no prior assignment. Our inverse graph construction exploits recurring frequency differences and four-cycle closures to assemble an energy-level network at kilohertz precision. The dense, broadband spectra this requires are produced by a cavity-enhanced spectrometer (SCALS) that scans continuously across tens of terahertz at kilohertz accuracy, combining broadband coverage, high sensitivity, and high precision in a single automated instrument. Applied to the water absorption spectrum in the range of 1537--1605~nm, 686 Lamb dips of water were obtained without assignments, and the method reconstructs 158 energy levels that are mostly two orders of magnitude more precise than the corresponding literature values. By removing the assignment barrier, this approach opens a route to exploratory precision spectroscopy of polyatomic molecules without a priori knowledge of transition frequencies.