Publikationstyp: Beitrag in wissenschaftlicher Zeitschrift
Art der Begutachtung: Peer review (Publikation)
Titel: Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer
Autor/-in: Adlhart, Christian
Uggerud, Einar
DOI: 10.1039/B516658F
Erschienen in: Physical Chemistry Chemical Physics
Band(Heft): 2006
Heft: 9
Seiten: 1066
Seiten bis: 1071
Erscheinungsdatum: 2006
Verlag / Hrsg. Institution: Royal Society of Chemistry
Verlag / Hrsg. Institution: London
ISSN: 1463-9076
Sprache: Englisch
Schlagwörter: Potential energy surface; Substitution reaction; Simulation and modeling; Proton transfer
Fachgebiet (DDC): 540: Chemie
Zusammenfassung: 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.
Volltext Version: Publizierte Version
Lizenz (gemäss Verlagsvertrag): Lizenz gemäss Verlagsvertrag
Departement: Life Sciences und Facility Management
Organisationseinheit: Institut für Chemie und Biotechnologie (ICBT)
Enthalten in den Sammlungen:Publikationen Life Sciences und Facility Management

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