| 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 |
| Seite(n): | 1066 |
| Seiten bis: | 1071 |
| Erscheinungsdatum: | 2006 |
| Verlag / Hrsg. Institution: | Royal Society of Chemistry |
| Verlag / Hrsg. Institution: | London |
| ISSN: | 1463-9076 1463-9084 |
| 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. |
| URI: | https://digitalcollection.zhaw.ch/handle/11475/2115 |
| 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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Adlhart, C., & Uggerud, E. (2006). Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer. Physical Chemistry Chemical Physics, 2006(9), 1066–1071. https://doi.org/10.1039/B516658F
Adlhart, C. and Uggerud, E. (2006) ‘Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer’, Physical Chemistry Chemical Physics, 2006(9), pp. 1066–1071. Available at: https://doi.org/10.1039/B516658F.
C. Adlhart and E. Uggerud, “Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer,” Physical Chemistry Chemical Physics, vol. 2006, no. 9, pp. 1066–1071, 2006, doi: 10.1039/B516658F.
ADLHART, Christian und Einar UGGERUD, 2006. Reaction dynamics simulations of the identity SN2 reaction H2O + HOOH2+ -> H2OOH+ + H2O : requirements for reaction and competition with proton transfer. Physical Chemistry Chemical Physics. 2006. Bd. 2006, Nr. 9, S. 1066–1071. DOI 10.1039/B516658F
Adlhart, Christian, and Einar Uggerud. 2006. “Reaction Dynamics Simulations of the Identity SN2 Reaction H2O + HOOH2+ -> H2OOH+ + H2O : Requirements for Reaction and Competition with Proton Transfer.” Physical Chemistry Chemical Physics 2006 (9): 1066–71. https://doi.org/10.1039/B516658F.
Adlhart, Christian, and Einar Uggerud. “Reaction Dynamics Simulations of the Identity SN2 Reaction H2O + HOOH2+ -> H2OOH+ + H2O : Requirements for Reaction and Competition with Proton Transfer.” Physical Chemistry Chemical Physics, vol. 2006, no. 9, 2006, pp. 1066–71, https://doi.org/10.1039/B516658F.
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