Unimolecular dissociations of CF3H into (1) CF2(1A1) + HF, (2) CF3 + H and (3) CF2H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), (2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.
Bibliographical noteFunding Information:
DNS gratefullya cknowledgetsh e financial support for the post-doctorafle llowshipfrom Korea Sciencea ndE ngineeringFo undationT.h is work was supportedb y the Ministry of Science and Technology.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry