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Issue 9, 2006
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Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ → H2OOH+ + H2O. Requirements for reaction and competition with proton transfer

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Abstract

Despite the fact that the transition structure of the gas phase SN2 reaction H2O + HOOH2+ → HOOH2+ + H2O is well below the reactants in potential energy, the reaction has not yet been observed by experiment. Variational transition state RRKM theory reveals a strong preference for the competing proton transfer reaction H2O + HOOH2+ → H3O+ + HOOH due to entropy factors. Born–Oppenheimer reaction dynamics simulations confirm these results. However, by increasing the collision energy to around 7.5 eV the probability for nucleophilic substitution increases relative to proton transfer. These observations are explained by the presence of the key common intermediate HOO(H)⋯H–OH2+ which leads to effective proton transfer, but can be avoided with increasing collision energy. However, the SN2 probability remains below 0.2 since successful passage through the TS requires optimum initial orientation of the reactants, excitation of the relative translational motion and good phase correlation between the O–O vibration and the motion of the incoming water.

Graphical abstract: Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ → H2OOH+ + H2O. Requirements for reaction and competition with proton transfer

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Publication details

The article was received on 08 Aug 2005, accepted on 22 Dec 2005 and first published on 10 Jan 2006


Article type: Paper
DOI: 10.1039/B516658F
Phys. Chem. Chem. Phys., 2006,8, 1066-1071

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    Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ → H2OOH+ + H2O. Requirements for reaction and competition with proton transfer

    C. Adlhart and E. Uggerud, Phys. Chem. Chem. Phys., 2006, 8, 1066
    DOI: 10.1039/B516658F

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