Rotational excitation of singly and doubly deuterated formaldehyde induced by collisions with molecular hydrogen

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Abstract
This work presents calculations of state-to-state collisional rate coefficients for the rotational excitation of the deuterated formaldehyde isotopologs, HDCO and D 2 CO, induced by collisions with molecular hydrogen, coupled with experimental verification by pressurebroadening measurements. Time-independent scattering calculations were performed using the close-coupling method to compute inelastic cross sections for collisions with both para- H 2 ( j 2 = 0) and ortho- H 2 ( j 2 = 1). These calculations are based on the H 2 CO–H 2 potential energy surface previously determined at the CCSD(T) level of theory and transformed to account for the isotopic substitution. The resulting rate coefficients cover the lowest 100 rotational states of HDCO and 60 states of ortho- and para- D 2 CO with internal energies less than 200 cm −1 . Collisional data were obtained for temperatures up to 100 K for HDCO and D 2 CO and extended up to 300 K using the coupled-states approximation. The computed rate coefficients show systematic differences between ortho- H 2 and para- H 2 collisions, with the former generally yielding larger values by a factor of 2–3. Rate coefficients for HDCO–H 2 are found to be lower by a factor of 2 to 3 compared to those of H 2 CO–H 2 and D 2 CO–H 2 . Pressure-broadening coefficients were also calculated using the random-phase approximation and compared with new laboratory measurements, yielding agreement by about 5–30%.
Funding Information
  • Institut Universitaire de France
  • Ministry of Education, Culture, Sports, Science and Technology (JP20H05844)
  • Ministry of Education, Culture, Sports, Science and Technology (JP20H05845)
  • Ministry of Education, Culture, Sports, Science and Technology (JP25H00676)
  • JSPS Bilateral Program Number (JPJSBP120243212)
  • HORIZON EUROPE Marie Sklodowska-Curie Actions (899546)
  • RIKEN Special Post Doctoral Researchers Program
  • PHC Sakura Program (51250NB)
  • Agence Nationale de la Recherche (ANR-24-CE30-3044)

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