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.; Troe, J.

doi:10.1021/acs.jpca.7b02415

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

Temperature and pressure dependences of the reactions of Fe⁺ with methyl halides CH₃X (X = Cl, Br, I): Experiments and kinetic modeling results.

MPS-Authors

/persons/resource/persons15934

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

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

2451236_Suppl.pdf
(Supplementary material), 385KB

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: https://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.