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Thermal Activation of Methane by MgO+: Temperature Dependent Kinetics, Reactive Molecular Dynamics Simulations and Statistical Modeling

Sweeny, Brendan C. and Pan, Hanqing and Kassem, Asmaa and Sawyer, Jordan C. and Ard, Shaun G. and Shuman, Nicholas S. and Viggiano, Albert A. and Brickel, Sebastian and Unke, Oliver T. and Upadhyay, Meenu and Meuwly, Markus. (2020) Thermal Activation of Methane by MgO+: Temperature Dependent Kinetics, Reactive Molecular Dynamics Simulations and Statistical Modeling. Physical Chemistry Chemical Physics, 00 (00). 00.

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Abstract

The kinetics of MgO + + CH 4 was studied experimentally using the variable ion source, temperature adjustable selected ion flow tube (VISTA-SIFT) apparatus from 300 − 600 K and computationally by running and analyzing reactive atomistic simula- tions. Rate coefficients and product branching fractions were determined as a function of temperature. The reaction proceeded with a rate of k = 5 . 9 ± 1 . 5 × 10 − 10 ( T/ 300 K) − 0 . 5 ± 0 . 2 cm 3 s − 1 . MgOH + was the dominant product at all temperatures, but Mg + , the co-product of oxygen-atom transfer to form methanol, was observed with a product branching fraction of 0 . 08 ± 0 . 03( T/ 300 K) − 0 . 8 ± 0 . 7 . Reactive molecular dynamics simulations using a reactive force field, as well as a neural network trained on thousands of structures yield rate coefficients about one order of magnitude lower. This underestimation of the rates is traced back to the multireference character of the transition state [MgOCH 4 ] + . Statistical modeling of the temperature-dependent kinetics provides further insight into the reactive potential surface. The rate limiting step was found to be consistent with a four-centered activation of the C-H bond, consistent with previous calculations. The product branching was modeled as a competition between dissociation of an insertion intermediate directly after the rate- limiting transition state, and traversing a transition state corresponding to a methyl migration leading to a Mg-CH 3 OH + complex, though only if this transition state is stabilized significantly relative to the dissociated MgOH + + CH 3 product channel. An alternative non-statistical mechanism is discussed, whereby a post-transition state bifurcation in the potential surface could allow the reaction to proceed directly from the four-centered TS to the Mg-CH 3 OH + complex thereby allowing a more robust competition between the product channels .
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Brickel, Sebastian and Unke, Oliver and Upadhyay, Meenu and Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:1463-9076
e-ISSN:1463-9084
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:15 Apr 2020 13:42
Deposited On:15 Apr 2020 13:42

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