Hyperfine-Resolved Near-Infrared Spectra of H₂¹⁷O

Huge efforts have recently been taken in the derivation of accurate compilations of rovibrational energies of water, one of the most important reference systems in spectroscopy. Such precision is desirable for all water isotopologues, although their investigation is challenged by hyperfine effects in their spectra. Frequency-comb locked noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS) allows for achieving high sensitivity, resolution, and accuracy. This technique has been employed to resolve the subtle hyperfine splittings of rovibrational transitions of H₂¹⁷O in the near-infrared region. Simulation and interpretation of the H₂¹⁷O saturation spectra have been supported by coupled-cluster calculations performed with large basis sets and accounting for high-level corrections. Experimental ¹⁷O hyperfine parameters are found in excellent agreement with the corresponding computed values. The need of including small hyperfine effects in the analysis of H₂¹⁷O spectra has been demonstrated together with the ability of the computational strategy employed for providing quantitative predictions of the corresponding parameters.