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Published December 22, 1989 | public
Journal Article

Picosecond dissociation of ketene: Experimental state-to-state rates and tests of statistical theories


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 2×10^8 s^(−1) is in agreement with the previous lower limit of 7×10^7 s^(−1) of Chen, Green and Moore.

Additional Information

© 1990 Elsevier Science Publishers B.V. Received 29 September 1989; in final form 5 October 1989. The authors would like to thank Professor Rudolph A. Marcus for helpful discussions, and Professor C. Bradley Moore for many helpful discussions and correspondence of unpublished results. We would also like to thank Amy Hoffman for assistance with some of the (000) measurements. This work was supported by a grant from the National Science Foundation CHE 8512887.

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