Spectroscopic-network-assisted precision spectroscopy and its application to water.

Tóbiás, Roland; Furtenbacher, Tibor; Simkó, Irén; Császár, Attila G; Diouf, Meissa L; Cozijn, Frank M J; Staa, Joey M A; Salumbides, Edcel J et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Frequency combs and cavity-enhanced optical techniques have revolutionized molecular spectroscopy: their combination allows recording saturated Doppler-free lines with ultrahigh precision. Network theory, based on the generalized Ritz principle, offers a powerful tool for the intelligent design and validation of such precision-spectroscopy experiments and the subsequent derivation of accurate energy differences. As a proof of concept, 156 carefully-selected near-infrared transitions are detected for H<sub>2</sub><sup>16</sup>O, a benchmark system of molecular spectroscopy, at kHz accuracy. These measurements, augmented with 28 extremely-accurate literature lines to ensure overall connectivity, allow the precise determination of the lowest ortho-H<sub>2</sub><sup>16</sup>O energy, now set at 23.794 361 22(25) cm<sup>-1</sup>, and 160 energy levels with similarly high accuracy. Based on the limited number of observed transitions, 1219 calibration-quality lines are obtained in a wide wavenumber interval, which can be used to improve spectroscopic databases and applied to frequency metrology, astrophysics, atmospheric sensing, and combustion chemistry.