Low energy H+CO scattering revisited CO rotational excitation with new potential surfaces

Context. A recent modeling study of brightness ratios for CO rotational transitions in gas typical of the diffuse ISM by Liszt found the role of H collisions to be more important than previously assumed. This conclusion was based on recent quantum scattering calculations using the so-called WKS potential energy surface (PES) which reported a large cross section for the important 0 → 1 rotational transition. This result is in contradiction to one obtained using the earlier BBH PES for which the cross section is quite small and which is consistent with an expected homonuclear-like propensity for even ΔJ transitions. Aims. We revisit this contradiction with new scattering calculations using two new ab initio PESs that focus on the important long-range behavior and explore the validity of the apparent departure from the expected even ΔJ propensity in H-CO rotational excitation obtained with the WKS PES. Methods. Close-coupling (CC) rigid-rotor calculations for CO(v = 0, J = 0) excitation by H are performed on four different PESs. Two of the PESs are obtained in this work using state-of-the-art quantum chemistry techniques at the CCSD(T) and MRCI levels of theory. Results. Cross sections for the J = 0 → 1, as well as other odd ΔJ, transitions are significantly suppressed compared to even ΔJ transitions in thermal energy CC calculations using the CCSD(T) and MRCI surfaces. This is consistent with the expected even ΔJ propensity and in contrast to CC calculations using the WKS PES which predict a dominating 0 → 1 transition. Conclusions. Inelastic collision cross section calculations are sensitive to fine details in the anisotropic components of the PES and its long-range behavior. The current results obtained with new surfaces for H-CO scattering suggest that the original astrophysical assumption that excitation of CO by H2 dominates the kinetics of CO in diffuse ISM gas is likely to remain valid. © ESO 2007.

Duke Scholars

Author Peng Zhang Chemistry