A comparative study of the low energy HD+o-/p-H2 rotational excitation/de-excitation collisions and elastic scattering

Physics – Chemical Physics

Scientific paper

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11 pages, 9 figures

Scientific paper

10.1063/1.3699203

The Diep and Johnson (DJ) H$_2$-H$_2$ potential energy surface (PES) obtained from the first principles [P. Diep, K. Johnson, J. Chem. Phys. 113, 3480 (2000); 114, 222 (2000)], has been adjusted through appropriate rotation of the three-dimensional coordinate system and applied to low-temperature ($T<300$ K) HD+$o$-/$p$-H$_2$ collisions of astrophysical interest. A non-reactive quantum mechanical close-coupling method is used to carry out the computation for the total rotational state-to-state cross sections $\sigma_{j_1j_2\rightarrow j'_1j'_2}(\epsilon)$ and corresponding thermal rate coefficients $k_{j_1j_2\rightarrow j'_1j'_2}(T)$. A rather satisfactory agreement has been obtained between our results computed with the modified DJ PES and with the newer H$_4$ PES [A.I. Boothroyd, P.G. Martin, W.J. Keogh, M.J. Peterson, J. Chem. Phys. 116, 666 (2002)], which is also applied in this work. A comparative study with previous results is presented and discussed. Significant differences have been obtained for few specific rotational transitions in the H$_2$/HD molecules between our results and previous calculations. The low temperature data for $k_{j_1j_2\rightarrow j'_1j'_2}(T)$ calculated in this work can be used in a future application such as a new computation of the HD cooling function of primordial gas, which is important in the astrophysics of the early Universe.

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