The unimolecular decomposition of vibrationally excited 1‐deuterio‐1,1,2‐trifluoroethane

Abstract

Abstract A study has been made of the unimolecular decomposition of the vibrationally excited molecule CF 2 DCFH 2 *, formed from the combination of CF 2 D and CFH 2 radicals. The α,β‐elimination channels lead to the products cis ‐ and trans ‐CFDCFH and CF 2 CH 2 and H(D)F. The α,α‐elimination channel produces cis and trans ‐CFHCFH and DF. The pressure dependencies of the various isomer ratios have been examined. For the α,α elimination the energy partitioning pattern is such that subsequent isomerization of the olefin product can occur. This, and previous work on CDCl 2 CH 2 Cl*, clearly show that the energy partitioning in α,α and α,β eliminations is very different. It is tentatively concluded that HF (from the CFH 2 group) and HD eliminations also take place.