OH-Stretching Overtone Induced Dynamics in HSO₃F from Reactive Molecular Dynamics Simulations

Brickel, Sebastian and Meuwly, Markus. (2017) OH-Stretching Overtone Induced Dynamics in HSO₃F from Reactive Molecular Dynamics Simulations. Journal of Physical Chemistry A, 121 (27). pp. 5079-5087.

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Official URL: https://edoc.unibas.ch/94259/

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The OH-stretch induced dynamics in fluorosulfonic acid (HSO 3 F) is characterized from a statistically significant number of trajectories using multisurface adiabatic reactive molecular dynamics (MS-ARMD) simulations. The global reactive potential energy surface, which describes H-transfer and HF-elimination, is parametrized at the MP2/6-311G++(2p,2d) level of theory with an accuracy of better than 1 kcal/mol. Excitation along the OH-local mode leads to H-transfer dynamics but elimination of HF is only observed for excitations with ν ≥ 6 for 1 out of 5000 trajectories. This finding differs fundamentally from the situation for vibrationally induced photodissociation of H 2 SO 4 and HSO 3 Cl, for which, even with excitations of 4 quanta along the OH-stretch mode, elimination of H 2 O and HCl, respectively, is readily observed on the subnanosecond time scale. RRKM rates for HX-elimination in HSO 3 X (X = F, Cl) only differ by a factor of 5. The findings from the reactive molecular dynamics simulations together with the RRKM results thus indicate that the origin for a closed HF-production channel is dynamical. This is also consistent with experimental findings for hydrofluoroethanes in shock tubes, which found pronounced non-RRKM behavior.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:19 Apr 2023 05:57
Deposited On:19 Apr 2023 05:57

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