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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.

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Troe,  J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

Ard, S. G., Shuman, N. S., Martinez Jr., O., Keyes, N. R., Viggiano, A. A., Guo, H., et al. (2017). Temperature and pressure dependences of the reactions of Fe+ with methyl halides CH3X (X = Cl, Br, I): Experiments and kinetic modeling results. Journal of Physical Chemistry A, 121(21), 4058-4068. doi:10.1021/acs.jpca.7b02415.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002D-5BF2-C
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 SN2 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.