Time-resolved Two-laser Probe of Cr(CO)6 Photodissociation Dynamics
Abstract
We have examined the photodissociation of jet-cooled Cr(CO)6 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 Cr(CO)4 via 248-nm photolysis of Cr(CO)6 is slower if the Cr(CO)6 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 Cr(CO)5 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 Cr(CO)6. We discuss the utility of our time-resolved MPD/atomic fluorescence technique as a general dynamical probe for metal carbonyl photodissociation.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 01, 1992
- Accession Number
- ADA250930
Entities
People
- James F. Garvey
- Robert Deleon
- William R. Peifer
Organizations
- University at Buffalo