Deformed transition-state theory : Deviation from Arrhenius behavior and application to bimolecular hydrogen transfer reaction rates in the tunneling regime
© 2016 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 38(2017), 3 vom: 30. Jan., Seite 178-188 |
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| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2017
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't d-Arrhenius hydrogen transfer non-Arrhenius sub-Arrhenius transition-state theory Hydrogen 7YNJ3PO35Z |
| Zusammenfassung: | © 2016 Wiley Periodicals, Inc. A formulation is presented for the application of tools from quantum chemistry and transition-state theory to phenomenologically cover cases where reaction rates deviate from Arrhenius law at low temperatures. A parameter d is introduced to describe the deviation for the systems from reaching the thermodynamic limit and is identified as the linearizing coefficient in the dependence of the inverse activation energy with inverse temperature. Its physical meaning is given and when deviation can be ascribed to quantum mechanical tunneling its value is calculated explicitly. Here, a new derivation is given of the previously established relationship of the parameter d with features of the barrier in the potential energy surface. The proposed variant of transition state theory permits comparison with experiments and tests against alternative formulations. Prescriptions are provided and implemented to three hydrogen transfer reactions: CH4 + OH → CH3 + H2 O, CH3 Cl + OH → CH2 Cl + H2 O and H2 + CN → H + HCN, widely investigated both experimentally and theoretically. © 2016 Wiley Periodicals, Inc |
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| Beschreibung: | Date Completed 22.08.2017 Date Revised 22.08.2017 published: Print-Electronic Citation Status MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.24529 |