Time-resolved Two-laser Probe of Cr(CO)6 Photodissociation Dynamics
STATE UNIV OF NEW YORK AT BUFFALO DEPT OF CHEMISTRY
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We have examined the photodissociation of jet-cooled CrCO6 using a time-resolved, two-laser multiphoton dissociation MPD technique with fluorescence detection of the atomic photofragments. We have observed that the rate of appearance of CrCO4 via 248-nm photolysis of CrCO6 is slower if the CrCO6 has first been cooled in a supersonic expansion. We suggest the difference in the observed rates is due to slower intersystem crossing in the transient CrCO5 following impulsive loss of the first CO ligand from the jet- cooled hexacarbonyl. This intersystem crossing is thought to be facilitated by low-energy OC-Cr-CO bending modes, which are probably not accessible by one- photon absorption from the ground state CrCO6. We discuss the utility of our time-resolved MPDatomic fluorescence technique as a general dynamical probe for metal carbonyl photodissociation.
- Organic Chemistry
- Radiation and Nuclear Chemistry
- Electricity and Magnetism
- Nuclear Physics and Elementary Particle Physics