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dc.contributor.authorAdlhart, Christian-
dc.contributor.authorUggerud, Einar-
dc.date.accessioned2018-01-18T10:42:45Z-
dc.date.available2018-01-18T10:42:45Z-
dc.date.issued2006-
dc.identifier.issn1463-9076de_CH
dc.identifier.issn1463-9084de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/2115-
dc.description.abstractDespite 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.de_CH
dc.language.isoende_CH
dc.publisherRoyal Society of Chemistryde_CH
dc.relation.ispartofPhysical Chemistry Chemical Physicsde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subjectPotential energy surfacede_CH
dc.subjectSubstitution reactionde_CH
dc.subjectSimulation and modelingde_CH
dc.subjectProton transferde_CH
dc.subject.ddc540: Chemiede_CH
dc.titleReaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transferde_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
zhaw.organisationalunitInstitut für Chemie und Biotechnologie (ICBT)de_CH
zhaw.publisher.placeLondonde_CH
dc.identifier.doi10.1039/B516658Fde_CH
zhaw.funding.euNode_CH
zhaw.issue9de_CH
zhaw.originated.zhawYesde_CH
zhaw.pages.end1071de_CH
zhaw.pages.start1066de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume2006de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
Appears in Collections:Publikationen Life Sciences und Facility Management

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