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Issue 13, 2017
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Isotopic and quantum-rovibrational-state effects for the ion–molecule reaction Image ID:c7cp00295e-t1.gif in the collision energy range of 0.03–10.00 eV

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Abstract

We report detailed quantum-rovibrational-state-selected integral cross sections for the formation of H3O+via H-transfer (σHT) and H2DO+via D-transfer (σDT) from the Image ID:c7cp00295e-t4.gif reaction in the center-of-mass collision energy (Ecm) range of 0.03–10.00 eV, where (v+1v+2v+3) = (000), (100), and (020) and Image ID:c7cp00295e-t5.gif. The Ecm inhibition and rotational enhancement observed for these reactions at Ecm < 0.5 eV are generally consistent with those reported previously for H2O+ + H2(D2) reactions. However, in contrast to the vibrational inhibition observed for the latter reactions at low Ecm < 0.5 eV, both the σHT and σDT for the H2O+ + HD reaction are found to be enhanced by (100) vibrational excitation, which is not predicted by the current state-of-the-art theoretical dynamics calculations. Furthermore, the (100) vibrational enhancement for the H2O+ + HD reaction is observed in the full Ecm range of 0.03–10.00 eV. The fact that vibrational enhancement is only observed for the reaction of H2O+ + HD, and not for H2O+ + H2(D2) reactions suggests that the asymmetry of HD may play a role in the reaction dynamics. In addition to the strong isotopic effect favoring the σHT channel of the H2O+ + HD reaction at low Ecm < 0.5 eV, competition between the σHT and σDT of the H2O+ + HD reaction is also observed at Ecm = 0.3–10.0 eV. The present state-selected study of the H2O+ + HD reaction, along with the previous studies of the H2O+ + H2(D2) reactions, clearly shows that the chemical reactivity of H2O+ toward H2 (HD, D2) depends not only on Ecm, but also on the rotational and vibrational states of H2O+(X2B1). The detailed σHT and σDT values obtained here with single rovibrational-state selections of the reactant H2O+ are expected to be valuable benchmarks for state-of-the-art theoretical calculations on the chemical dynamics of the title reaction.

Graphical abstract: Isotopic and quantum-rovibrational-state effects for the ion–molecule reaction in the collision energy range of 0.03–10.00 eV

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Publication details

The article was received on 14 Jan 2017, accepted on 06 Mar 2017 and first published on 07 Mar 2017


Article type: Paper
DOI: 10.1039/C7CP00295E
Citation: Phys. Chem. Chem. Phys., 2017,19, 8694-8705
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    Isotopic and quantum-rovibrational-state effects for the ion–molecule reaction Image ID:c7cp00295e-t1.gif in the collision energy range of 0.03–10.00 eV

    Y. Xu, B. Xiong, Y. C. Chang and C. Y. Ng, Phys. Chem. Chem. Phys., 2017, 19, 8694
    DOI: 10.1039/C7CP00295E

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