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Picosecond laser studies of the effects of reactants on intramolecular energy relaxation of diphenylcarbene: Reaction of diphenylcarbene with alcohols

✍ Scribed by E.V. Sitzmann; J.G. Langan; K.B. Eisenthal


Publisher
Elsevier Science
Year
1984
Tongue
English
Weight
523 KB
Volume
112
Category
Article
ISSN
0009-2614

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✦ Synopsis


Picosecond laser induced fluorescence measurements provide for the first time the direct meanrrement of the intramolccular and intermolecular energy decay dynamics of singlet diphenylcarbene (' DPC) in the presence of reactive molecules. As exemplified by the reaction of ' DPC with alcohols it is found that reactive molecules provide ' DPC witi not only a chemical decay channel but also an intramolecular decay channel which is due to a solvent polarity effect. These chemical and physical effects can act in opposite directions leading to novel results such as a sigtificaat increase in the sin$et state lifetime upon addition of reacting molecules. The absolute reaction rate constants of 'DPC with alcohols, in different solvents, obtained by direct measurements are also reported.


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