Reactions of H-2, HD, and D-2 with H-2(+), HD+, and D-2(+): Product-Channel Branching Ratios and Simple Models

JOURNAL OF PHYSICAL CHEMISTRY LETTERS(2022)

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Abstract
present measurements of the product-channel branching ratios of the reactions (i) HD+ + HD forming H2D+ + D (38.1(30)%) and HD2+ + H (61.9(30)%), (ii) HD+ + D-2 forming HD2+ + D (61.4(35)%) and D-3(+) + H (38.6(35)%), and (iii) D-2(+) + HD forming HD2++ D (60.5(20)%) and D-3(+) + H (39.5(20)%) at collision energies Ecoll near zero, i.e., below k(B) x 1 K. These branching ratios are compared with branching ratios predicted using three simple models: a combinatorial model (M1), a model (M2) describing the reactions as H-, H+-, D-, and D+-transfer processes, and a statistical model (M3) that relates the reaction rate coefficients to the translational and rovibrational state densities of the HnD3-n+ + H/D (n = 0, 1, 2 or 3) product channels. The experimental data are incompatible with the predictions of models M1 and M2 and reveal that the branching ratios exhibit clear correlations with the product state densities.
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Key words
reactions,product-channel
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