The state-to-state dissociation rates of ketene have been measured for a variety of singlet methylene rotational states in both the ground and (010) vibrational levels of the methylene fragment. Measured time constants range from 1.0 ns at 500 cm-1 to 19 ps at 5600 cm-1 above threshold. The measurements cannot be accounted for by simple phase space theory (PST), which has been used to explain product state distributions, or tight transition state RRKM theory, but are in good agreement with variational RRKM theory. The estimated threshold rate of 2×108 s-1 is in agreement with the previous lower limit of 7×107 s-1 of Chen, Green and Moore.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry