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\title{EXPERIMENTAL VALIDATION OF CO$_2$ LINE LISTS IN THE SPECTRAL RANGE NEAR 0.69 $\mu$m}

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\author{\underline{\FirstName K. \LastName BIELSKA},
  \FirstName A.~A. \LastName BALASHOV, \FirstName S. \LastName W\'{O}JTEWICZ, \FirstName R. \LastName CIURY{\L}O, \FirstName D. \LastName LISAK}
\address{Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University in Toru\'n, Grudziadzka 5, 87-100 Torun, Poland}

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\address{Department of Applied Chemistry and Institute of Molecular Science, National Yang Ming Chiao Tung University, Hsinchu, Taiwan 30010}

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\fancyhead[C]{{\footnotesize \textit{HRMS, 28th Colloquium, Dijon, France,
  Aug. 28 - Sept. 1, 2023}}}
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We conducted an attempt to measure CO$_2$ lines in the spectral range between 0.687 and 0.699 $\mu$m. The predicted line intensities are below $2.1\times10^{-30}$~\intun. To detect these weak lines we employed a cavity ring-down spectroscopy (CRDS) technique. 
It was already shown that our spectrometer has sufficient sensitivity to measure a CO line having intensity of \mbox{$1.807\times10^{-30}$} \intun\ with a signal-to-noise ratio of 36 if very high-reflectivity ring-down cavity mirrors are used\footnote{A.A. Balashov {\it et al.}, Measurement and calculation of CO (7--0) overtone line intensities, accepted in J. Chem. Phys.}.

CO$_2$ lines having intensities of up to $2.076\times10^{-30}$ \intun\ are predicted by the ExoMol\footnote{\href{http://dx.doi.org/10.1093/mnras/staa1874}{doi:10.1093/mnras/staa1874}, S.N. Yurchenko {\it et al.}, ExoMol line lists - XXXIX. Ro-vibrational molecular line list for CO$_2$, Mon. Not. R. Astron. Soc. 496, 5282-5291 (2020).} line list and available in the HITRAN 2020\footnote{\href{http://dx.doi.org/10.1016/j.jqsrt.2021.107949}{doi:10.1016/j.jqsrt.2021.107949}, I.E. Gordon {\it et al.}, The HITRAN2020 molecular spectroscopic database, J. Quant. Spectrosc. Radiat. T. 277, 107949 (2022).} database. Also, the Ames-2021 line list\footnote{\href{http://dx.doi.org/10.1021/acs.jpca.2c01291}{doi:10.1021/acs.jpca.2c01291}, X. Huang {\it et al.}, Ames-2021 CO$_2$ dipole moment surface and IR line lists: toward 0.1\% uncertainty for CO$_2$ IR intensities, J. Phys. Chem. A 126, 5940-5964 (2022)} contains lines located in this spectral range having intensities up to $1.819\times10^{-31}$~\intun. We probed altogether five spectral ranges corresponding to relatively strong lines among ones predicted by both line lists. Within these ranges, there are expected more than twenty CO$_2$ lines. Our estimated detection limit in the case of each probed spectral range is between 2 and above 10 times lower than the expected peak absorption level. However, none of these lines was detected in our experiment.
Our result is in contrast to recent FTS measurements\footnote{\href{http://dx.doi.org/10.1016/j.jqsrt.2023.108595}{doi:10.1016/j.jqsrt.2023.108595}, O.M. Lyulin {\it et al.}, The absorption bands of $^{12}$C$^{16}$O$_2$ near 718 nm, J. Quant. Spectrosc. Radiat. T. 303, 108595 (2023).} for two orders of magnitude stronger CO$_2$ bands at slightly higher wavelengths.  
However, in the case of the HITRAN database, lines detected with the FTS are predicted by a different set of calculations than the ones that we intended to measure. 


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