High sensitivity absorption spectroscopy of acetylene near 1.2 µm

Abstract

The weak high-resolution absorption spectrum of natural acetylene has been recorded by high sensitivity cavity ring down spectroscopy (CRDS) near 1.2 µm. The frequency scale of the spectra was obtained by coupling the CRDS spectrometer to a self-referenced frequency comb. The room temperature recordings, performed at a pressure of 10.0 Torr, cover the 8210–8670 cm−1 spectral interval. A list of more than 11,000 lines was constructed in the region. The smallest intensity values are on the order of 10−29 cm/molecule which is more than two orders of magnitude smaller than previous measurements by Fourier transform spectroscopy (FTS). More than 2600 lines were rovibrationally assigned using previous observations and predictions based on the effective operator approach. They include 2270, 338 and 28 absorption lines of 12C2H2, 12C13CH2 and 12C2HD, respectively, belonging to a total of 52 vibrational bands, thirty-six of them being newly reported. For comparison, the HITRAN2016 database provides line parameters of only two 12C2H2 bands, in the same region. Spectroscopic parameters of the upper vibrational levels were derived from standard band-by-band fits of the line positions (typical rms values of the (obs.-calc.) deviations are better than 0.002 cm–1). The vibrational transition dipole moment squared and Herman-Wallis coefficients of 39 bands were derived from a fit of the intensity values measured in this work and combined with previous FTS data for the strongest bands. A recommended list is constructed in the region using calculated line parameters for the unperturbed bands and experimental positions and intensities for the others. The recommended list including a total of 3139 transitions will help to complete acetylene spectroscopic databases in the near-infrared.