Temperature and Pressure Dependences of the Reactions of Fe+ with Methyl Halides CH3X (X = Cl, Br, I): Experiments and Kinetic Modeling Results
2017 | journal article. A publication with affiliation to the University of Göttingen.
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Temperature and Pressure Dependences of the Reactions of Fe+ with Methyl Halides CH3X (X = Cl, Br, I): Experiments and Kinetic Modeling Results
Ard, S. G.; Shuman, N. S.; Martinez, O. J.; Keyes, N. R.; Viggiano, A. A.; Guo, H. & Troe, J. (2017)
The Journal of Physical Chemistry A, 121(21) pp. 4058-4068. DOI: https://doi.org/10.1021/acs.jpca.7b02415
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- Authors
- Ard, Shaun G.; Shuman, Nicholas S.; Martinez, Oscar, Jr.; Keyes, Nicholas R.; Viggiano, Albert A.; Guo, Hua; Troe, Juergen
- Abstract
- The pressure and temperature dependences of the reactions of Fe+ with methyl halides CH3X (X = Cl, Br, I) in He were measured in a selected ion flow tube over the ranges 0.4 to 1.2 Torr and 300-600 K. FeX+ was observed for all three halides and FeCH3+ was observed for the CH3I reaction. FeCH3X+ adducts (for all X) were detected in all reactions. The results were interpreted assuming two-state reactivity with spin-inversions between sextet and quartet potentials. Kinetic modeling allowed for a quantitative representation of the experiments and for extrapolation to conditions outside the experimentally accessible range. The modeling required quantum-chemical calculations of molecular parameters and detailed accounting of angular momentum effects. The results show that the FeX+ products come via an insertion mechanism, while the FeCH3+ can be produced from either insertion or S(N)2 mechanisms, but the latter we conclude is unlikely at thermal energies. A statistical modeling cannot reproduce the competition between the bimolecular pathways in the CH3I reaction, indicating that some more direct process must be important.
- Issue Date
- 2017
- Status
- published
- Publisher
- Amer Chemical Soc
- Journal
- The Journal of Physical Chemistry A
- ISSN
- 1089-5639