Picosecond Laser Chemistry in Supersonic Jet Beams

In this review we describe the development and the applications of the picosecond-jet technique, which utilizes a picosecond laser and a supersonically-cold jet beam of large molecules. The applications include studies of coherence (quantum beats), photodissociation, isomerization, and partial solvation. The results emphasize the role of intramolecular energy redistribution, and provide evidence for intramolecular threshold effect for rates vs. excess molecular energy. Simple theory for this redistribution of energy among certain modes in molecules is given, and comparison with RRKM calculation is also made to assess the nature of the statistical behavior for the redistribution.