PICOSECOND TRANSIENT RAMAN INVESTIGATION OF THE ROLE OF VIBRATIONAL ENERGY IN THE ULTRAFAST PHOTODISSOCIATION OF CHROMIUM HEXACABONYL IN SOLUTION

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1990

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Ohio State University

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The ultrafast photochemistry of Cr(CO)6 has been the subject of recent controversy. Picosecond transient Raman spectroscopy has been used to study the photodissociation of $Cr(CO)_{6}$ at 266nm. It is found that the appearance time of the vibrationally cold hexacarbonyl photoproduct is rate limited by vibrational relaxation. The dynamics of the Stokes and anti-Stokes Raman spectrum indicate that vibrational cooling occurs on a remarkably long time scale requiring over 100ps for complete thermalization Solvent coordination of the photoproducts is directly observed in the Raman spectrum and is found to occur in $\le 5ps$ for hydrocarbon solvents.

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Author Institution: Department of Chemistry, Louisiana State University

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