The born approximation as a simple diagnostic method for direct molecular collisions with applications to Cl + HI and F + H2 reactions

Born approximation computations are presented and discussed for the Cl + HI → I + HCl and F + H₂ → H + HF reactions and their isotopic analogues. Most aspects of the role of reagent energy or the energy disposal in the products previously deduced from experiment or trajectory computations can be accounted for the Born approximation. The procedure used here neglects the interaction between non-bonded atoms. It does thereby provide a very simple computational scheme which requires as input only the spectroscopic constants of the reactants and products. In addition it offers simple qualitative interpretations of the trends in the results. The overall satisfactory agreement between the present results and past studies lends credibility to the basic propensity rule provided by the Born approximation: The most probable transitions are those that minimize the momentum transfer to the nuclei. The principle is discussed with special reference to exothermic (E′_T ? E_T) and endothermic transitions.The computations for Cl + HI indicate a decline of the reaction cross section with increasing kinetic energy and a strong enhancement by HI rotational energy. The surprisal analysis confirms the absence of vibrational population inversion for endothermic transitions. For the F + H₂ (and isotopic variants) reactions, the product-rotational state distribution extends nearly to the energy cut-off. The vibrational state distribution is somewhat different for para- and normal H₂ and, in general, the collision outcome is very sensitive to the initial rotational state of H₂ particularly at low translational energies. The HF/DF branching ratio is F + HD collisions is increasing with increase of the HD rotational state. The vibrational surprisal is essentially isotopically invariant.