English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Shock wave and theoretical modeling study of the dissociation of CH2F2 I. Primary processes.

MPS-Authors
/persons/resource/persons132811

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

/persons/resource/persons127684

Tellbach,  E.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

/persons/resource/persons15934

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

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Cobos, C. J., Hintzer, K., Sölter, L., Tellbach, E., Thaler, A., & Troe, J. (2017). Shock wave and theoretical modeling study of the dissociation of CH2F2 I. Primary processes. Journal of Physical Chemistry A, 121(41), 7813-7819. doi:10.1021/acs.jpca.7b05854.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002D-FCC1-B
Abstract
The unimolecular dissociation of CH2F2 leading to CF2 + H2, CHF + HF, or CHF2 + H, is investigated by quantum chemical calculations and unimolecular rate theory. Modeling of the rate constants is accompanied by shock wave experiments over the range 1400 – 1800 K monitoring the formation of CF2. It is shown that the energetically most favorable dissociation channel leading to CF2 + H2 has a higher threshold energy than the energetically less favorable one leading to CHF + HF. Falloff curves of the dissociations are modeled. Under the conditions of the described experiments, the primary dissociation CH2F2 → CHF + HF is followed by a reaction CHF + HF → CF2 + H2. The experimental value of the rate constant of the latter indicates that this reaction does not proceed by an addition-elimination process as assumed before, but by a more direct abstraction pathway involving elements of roaming dynamics.