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Accurate absolute frequency measurement of the S(2) transition in the fundamental band of H 2 near 2.03 μm.

D MondelainL Boux de CassonH FleurbaeySamir KassiAlain Campargue
Published in: Physical chemistry chemical physics : PCCP (2023)
A series of spectra of the quadrupolar electric S(2) transition of H 2 in the 1-0 band near 4917 cm -1 has been recorded at seven pressure values between 2 and 100 Torr. The comb-referenced cavity ring down spectroscopy (CR-CRDS) technique was used for the recording of this very weak transition. The accuracy of the spectrum frequency axis is achieved by linking the CRDS setup to an optical frequency comb referenced to a GPS-referenced 10 MHz rubidium clock. Applying a multi-spectrum fit procedure to the seven averaged spectra with a quadratic speed dependence Nelkin-Ghatak profile, the transition frequency is determined ( ν 0 = 147 408 142 357 kHz) with an uncertainty of 150 kHz (∼1 × 10 -9 in relative). This represents the smallest uncertainty achieved so far for a transition in the fundamental band of H 2 . The experimental frequency reported in this work is 1.53 MHz higher than the best-to-date theoretical value. This difference represents 1.5 times the 1 σ -uncertainty (about 1 MHz) of the calculated frequency. The measurements also allow for the determination of the absolute intensity value of the S(2) line which shows an agreement with the ab initio value at the per mil level. In addition, the cross section of the collision induced absorption (CIA) underlying the S(2) line is accurately retrieved from the quadratic pressure dependence of the baseline level of the recorded spectra.
Keyphrases
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