Publication type: Article in scientific journal
Type of review: Peer review (publication)
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
DOI: 10.1039/B516658F
Published in: Physical Chemistry Chemical Physics
Volume(Issue): 2006
Issue: 9
Pages: 1066
Pages to: 1071
Issue Date: 2006
Publisher / Ed. Institution: Royal Society of Chemistry
Publisher / Ed. Institution: London
ISSN: 1463-9076
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.
Fulltext version: Published version
License (according to publishing contract): Licence according to publishing contract
Departement: Life Sciences and Facility Management
Organisational Unit: Institute of Chemistry and Biotechnology (ICBT)
Appears in Collections:Publikationen Life Sciences und Facility Management

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