Abstract

The room temperature spectrum of the very weak third overtone band of carbon monoxide in natural isotopic abundance is recorded by cavity ring down spectroscopy (CRDS) referenced to a frequency comb, between 8206 and 8465 cm−1. The sensitivity of the recordings (noise equivalent absorption on the order of αmin ∼ 5 × 10−12 cm−1) allowed for measuring lines with intensity as weak as 1 × 10−30 cm/molecule at a recording pressure limited to 10.0 Torr. The use of low pressure values (1.0 and 10.0 Torr) helped to minimize the impact of profile effects on the derived line positions and line intensities. The line profile analysis was performed using the speed dependent Nelkin-Ghatak model for the 10 Torr recordings while the Voigt profile was found sufficient to account for the line shapes recorded at 1.0 Torr.Overall, line parameters of 227 transitions are derived. The observed transitions belong to the 4-0 band of the 12C16O, 13C16O, 12C18O and 12C17O isotopologues present in natural abundance in the sample and to the 5-1 hot band of 12C16O. For a large part of the observations, line positions are reported with accuracy as good as 4 × 10−6 cm−1 (∼120 kHz). The self-induced line shift of the 4-0 band is reported for the first time from the position values at 1 and 10 Torr. Using literature values of the 1-0, 2-0 and 3-0 bands, the vibrational dependence of the self-induced pressure shift in CO is discussed. The experimental values of the 12C16O v = 4 energy levels J < 26 are reproduced with a standard deviation of 2.5 × 10−6 cm−1 (75 kHz). The intensities of the 12C16O lines reported with an accuracy better than 1% show an overall good agreement with literature values in particular with those included in the HITRAN database.

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