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    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 4805-4816 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoisomerization of diphenylbutadiene was studied by picosecond absorption spectroscopy over wide pressure and temperature ranges in liquid and supercritical alkanes, CO2, SF6, and He. The reaction shows typical features of a thermal unimolecular reaction on the S1 potential energy surface. The rate can be expressed by a combination of standard unimolecular rate theory and Kramers–Smoluchowski theory. However, multidimensional behavior manifests itself in the transition to the gas phase low pressure range as well as to the high density Kramers–Smoluchowski range: in the former case, the low pressure limit of a unimolecular reaction of the polyatomic molecule is approached; in the latter case, the effective imaginary barrier frequency shows a marked apparent temperature dependence. The experiments also suggest contributions of reactant–solvent cluster interactions, which modify the barrier height even in nonpolar solvents.
    Type of Medium: Electronic Resource
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