Title: Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer
Authors : Adlhart, Christian
Uggerud, Einar
Published in : Physical Chemistry Chemical Physics
Issue : 9
Pages : 1066
Pages to: 1071
Publisher / Ed. Institution : Royal Society of Chemistry
Publisher / Ed. Institution: London
Issue Date: 2006
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
Language : English
Subjects : Potential energy surface; Substitution reaction; Simulation and modeling; Proton transfer
Subject (DDC) : 540: Chemistry
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 obsd. by expt. 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.
Departement: Life Sciences und Facility Management
Organisational Unit: Institute of Chemistry and Biotechnology (ICBT)
Publication type: Article in scientific Journal
DOI : 10.1039/B516658F
ISSN: 1463-9076
URI: https://digitalcollection.zhaw.ch/handle/11475/2115
Appears in Collections:Publikationen Life Sciences und Facility Management

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