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Published May 1, 1984 | Published
Journal Article Open

Unimolecular reaction rates in solution and in the isolated molecule: Comparison of diphenyl butadiene nonradiative decay in solutions and supersonic jets


The recent study of diphenyl butadiene (DPB) in supersonic jets and in solution by Shepanski et al.(1) and by Courtney and Felming(2), respectively, provides an opportunity to compare the isomerization rates measured in the isolated molecule (jet) with those measured at very low viscosity in solution. These comparisons should shed light on the vibrational energy flows between "optical" and "reactive" modes in the isolated molecule and on the connection between activated, friction dependent, models of barrier crossing in solution,(3-5) and statistical RRK (or RRKM) theories of gas phase unimolecular reactions(6).

Additional Information

© 1984 American Institute of Physics. Received 24 January 1984; accepted 29 February 1984. This work was supported by grants from the National Science Foundation to G.R.F. and A.H.Z. [A.H.Z. was a] Camille & Henry Dreyfus Foundation Teacher-Scholar. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 6693.

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