PRODUCTION OF EXCITED Cr ATOMS BY VISIBLE/UV MULTIPHOTOH DISSOCIATION OF $Cr(CO)_{6}$: Cr EMISSION ANALYSIS

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1982

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Ohio State University

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The multiphoton dissociation of $Cr(CO)_{6}$ has been studied by monitoring the emission spectra of the resulting excited Cr(I) atoms. A great deal of recent work has been dedicated to elucidating the mechanism for photodecomposition of organometallic compounds. Ideally, this involves measuring the product distribution as a function of excitation wavelength. Using known oscillator strengths for the atomic transitions, the relative fluorescence intensities arising from different atomic states allows us to calculate the distribution of states originally produced upon photodissociation by the tunable pulsed dye laser. The flux dependence of the atom yield also sheds light on the mechanism of photodissociation. These experiments are an excellent complement to similar multiphoton ionization (HPI) $studies^{1, 2}$ in that the ionization step is eliminated from the probe process so that the laser wavelengths can be detuned from atomic transitions. This allows atomic fragment state distributions to be measured quantitatively. Contrary to the HPI studies, our results show conclusively that photodissociation does not yield spin differentiated Cr(I) states, since omission from states of both even and odd parity is observed.

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$^{1}$S.P. Gerrity, L.J. Rothberg, and V. Veronica, Chem. Phys. Lett. 74, 1(1980). $^{2}$G.J. Pisanick, A. Gedanken, T.S. Bichelberger IV, N.A. Kuebler, and M.B. Robin, J. Chem. Phys. 75, 5215 (1981).

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