A crossed laser-molecular beam study of the photodissociation dynamics of Fe(CO)5 at 193 nm

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Abstract
A crossed laser‐molecular beam study of the photodissociation mechanism of Fe(CO)5 has been performed at 193 nm where time‐of‐flight measurements of the primary iron containing photofragments have been recorded under collision free conditions. The center‐of‐mass velocity distributions derived from the TOF data by the method of moments show that Fe(CO)2 accounts for >99% of all photoproducts formed after absorption of one photon. The only mechanism which quantitatively reproduces the measured velocity distributions is a sequence of three, uncorrelated, statistical CO eliminations. At high photon flux, a second photon can be absorbed by the Fe(CO)2 photofragment which decomposes by an uncorrelated sequential elimination of the remaining two CO ligands.

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