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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 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.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-5BF2-C Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-5BFC-7
Genre: Journal Article

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 Creators:
Ard, S. G., Author
Shuman, N. S., Author
Martinez Jr., O., Author
Keyes, N. R., Author
Viggiano, A. A., Author
Guo, H., Author
Troe, J.1, Author              
Affiliations:
1Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              

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 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.

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Language(s): eng - English
 Dates: 2017-05-192017-06-01
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1021/acs.jpca.7b02415
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Title: Journal of Physical Chemistry A
Source Genre: Journal
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Pages: - Volume / Issue: 121 (21) Sequence Number: - Start / End Page: 4058 - 4068 Identifier: -