Reactions of H2, HD, and D2 with H2+, HD+, and D2+: Product-Channel Branching Ratios and Simple Models. Merkt, F., Höveler, K., & Deiglmayr, J. The Journal of Physical Chemistry Letters, January, 2022. Publisher: American Chemical SocietyPaper doi abstract bibtex We 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+ + D2 forming HD2+ + D (61.4(35)%) and D3+ + H (38.6(35)%), and (iii) D2+ + HD forming HD2++ D (60.5(20)%) and D3+ + H (39.5(20)%) at collision energies Ecoll near zero, i.e., below kB × 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.
@article{merkt_reactions_2022,
title = {Reactions of {H2}, {HD}, and {D2} with {H2}+, {HD}+, and {D2}+: {Product}-{Channel} {Branching} {Ratios} and {Simple} {Models}},
shorttitle = {Reactions of {H2}, {HD}, and {D2} with {H2}+, {HD}+, and {D2}+},
url = {https://doi.org/10.1021/acs.jpclett.1c03374},
doi = {10.1021/acs.jpclett.1c03374},
abstract = {We 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+ + D2 forming HD2+ + D (61.4(35)\%) and D3+ + H (38.6(35)\%), and (iii) D2+ + HD forming HD2++ D (60.5(20)\%) and D3+ + H (39.5(20)\%) at collision energies Ecoll near zero, i.e., below kB × 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.},
urldate = {2022-01-21},
journal = {The Journal of Physical Chemistry Letters},
author = {Merkt, Frédéric and Höveler, Katharina and Deiglmayr, Johannes},
month = jan,
year = {2022},
note = {Publisher: American Chemical Society},
keywords = {Cold chemistry, Cold molecules},
pages = {864--871},
}
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