Ab initio quantum scattering calculations and a new potential energy surface for the HCl($X^1\Sigma^+$)-O$_{2}$($X^3\Sigma^-_g$) system: collision-induced line-shape parameters for O$_{2}$-perturbed R(0) 0-0 line in H$^{35}$Cl

The remote sensing of abundance and properties of HCl -- the main atmospheric reservoir of Cl atoms which directly participate in ozone depletion -- are important for monitoring the partitioning of chlorine between "ozone-depleting" and "reservoir" species. Such remote studies require knowledge of the shapes of molecular resonances of HCl, which are perturbed by collisions with the molecules of the surrounding air. In this work, we report the first fully quantum calculations of collisional perturbations of the shape of a pure rotational line in H$^{35}$Cl perturbed by an air-relevant molecule (as the first model system we choose the R(0) line in HCl perturbed by O$_2$). The calculations are performed on our new highly-accurate HCl($X^1\Sigma^+$)-O$_2$($X^3\Sigma^-_g$) potential energy surface. In addition to pressure broadening and shift, we determine also their speed dependencies and the complex Dicke parameter. This gives important input to the community discussion on the physical meaning of the complex Dicke parameter and its relevance for atmospheric spectra (previously, the complex Dicke parameter for such systems was mainly determined from phenomenological fits to experimental spectra and the physical meaning of its value in that context is questionable). We also calculate the temperature dependence of the line-shape parameters and obtain agreement with the available experimental data. We estimate the total combined uncertainties of our calculations at 2% relative RMSE residuals in the simulated line shape at 296~K. This result constitutes an important step towards computational population of spectroscopic databases with accurate ab initio line-shape parameters for molecular systems of terrestrial atmospheric importance.
Comment: 15 pages, 7 figures, The following article has been accepted by The Journal of Chemical Physics. After it is published, it will be found at https://pubs.aip.org/aip/jcp