Journal of Molecular Modeling

, Volume 17, Issue 3, pp 415–422 | Cite as

Ab initio studies on the decomposition kinetics of CF3OCF2O radical

Original Paper
First Online:
Received:
Accepted:

Abstract

The present study deals with the decomposition of CF3OCF2O radical formed from a hydrofluoroether, CF3OCHF2 (HFE-125), in the atmosphere. The study is performed using ab initio quantum mechanical methods. Two plausible pathways of decomposition of the titled species have been considered, one involving C-O bond scission and the other occurring via F atom elimination. The geometries of the reactant, products and transition states involved in the decomposition pathways are optimized and characterized at DFT (B3LYP) level of theory using 6-311G(d,p) basis set. Single point energy calculations have been performed at G2M(CC,MP2) level of theory. Out of the two prominent decomposition channels considered, the C-O bond scission is found to be dominant involving a barrier height of 15.3 kcal mol−1 whereas the F-elimination path proceeds with a barrier of 26.1 kcal mol−1. The thermal rate constants for the above two decomposition pathways are evaluated using canonical transition state theory (CTST) and these are found to be 1.78 × 106 s−1 and 2.83 × 10−7 s−1 for C-O bond scission and F-elimination respectively at 298 K and 1 atm pressure. Transition states are searched on the potential energy surfaces involved during the decomposition channels and each of the transition states is characterized. The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation.

Keywords

Canonical Transition State Theory Decomposition of HFE HFE-125 PES 
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Notes

Acknowledgments

One of the authors (BKM) is thankful to University Grants Commission, New Delhi for providing financial assistance under its Department of Special Assistance / Basic Scientific Research Program sanctioned to the Department of Chemistry, Deendayal Upadhyay Gorakhpur University, Gorakhpur. Authors are thankful to the reviewer for making valuable comments.

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  1. 1.Department of ChemistryDDU Gorakhpur UniversityGorakhpurIndia

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