English

Comprehensive \textsl{Ab Initio}~Calculations of \ce{CO2-H2} and \ce{CO2-He} Collisional Properties

Chemical Physics 2025-10-07 v1 Earth and Planetary Astrophysics

Abstract

We present comprehensive \textsl{ab initio} calculations of CO2_{\rm 2}-H2_{\rm 2} and CO2_{\rm 2}-He collisional properties from first principles, employing CCSD(T), potential calculations together with close-coupling dynamical scattering in the \YUMI~framework. We derive (in)elastic cross sections, rate coefficients, and pressure-broadening parameters -- incl., their rotational dependence up to m=50|m|=50, and temperature dependence over the range of 100-800 K. We provide Pad\'e fits for the broadening coefficients as a function of rotational quantum number, enabling extrapolation of the results and integration into spectroscopic databases, including HITRAN and HITEMP. The computed potentials for both CO2_{\rm 2}-H2_{\rm 2} and CO2_{\rm 2}-He have a sub-percent precision, and the dynamics-solving code YUMI ultimately yields the collisional parameters. Among these, the scaled pressure broadening experimental values meet the 10\% precision requirement for exoplanetary sciences with \textit{JWST}. This contrasts with the parameters available before the present calculations, which at higher temperatures (T>>400 K) deviate as much as 5×\times from the desired precision requirement. All derivations and collisional properties are provided with this manuscript, establishing the first of such a comprehensive ab initio foundation for collisional systems with a target molecule having more than two atoms.

Keywords

Cite

@article{arxiv.2510.03327,
  title  = {Comprehensive \textsl{Ab Initio}~Calculations of \ce{CO2-H2} and \ce{CO2-He} Collisional Properties},
  author = {Prajwal Niraula and Laurent Wiesenfeld and Nejmeddine Jaïdane and Julien de Wit and Robert J. Hargreaves and Jeremy Kepner and Deborah Woods and Cooper Loughlin and Iouli E. Gordon},
  journal= {arXiv preprint arXiv:2510.03327},
  year   = {2025}
}

Comments

Submitted. Comments welcome. Data available at zenodo: https:/zenodo.org/records/17161891