SPIN-ORBIT BRANCHING RATIO OF Cl ATOMS PRODUCED IN THE PHOTODISSOCIATION OF HCl.

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1995

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Ohio State University

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Abstract

The ratio of the populations of $Cl(^{2}P_{1/2})$ to $Cl(^{2}P_{3/2})$ produced in the photodissociation of HCl was measured as a function of excitation energy. Three photons were used to excite HCl to the $A'\Pi$ continuum state, while two photons were used to populate ten predissociating Rydberg states Multi-photon velocity-aligned Doppler spectroscopy was used to characterize the energetics and symmetry of the two-photon transitions. The $A^{1}\Pi$ results will be compared with the calculations of $Alexander et. al.^{1}$ and Givertz and $Balint-Kurti^{2}$. The Rydberg states displayed complex behavior. Some of the states gave a statistical branching ratio, others yielded primarily $Cl(^{2}P_{3/2})$, while still others gave comparable amounts of both Cl states. In some cases the branching ratio varied with rotational angular momentum.

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1. M. H. Alexander, B. Pouilly, and T. Duhoo, J. Chem. Phys. 99. 1752 (1993). 2. S. C. Givertz and G. G. Balint-Kurti, J. Chem. Soc., Faraday Trans. 2, 82, 1231 (1986).
Author Institution: University of Illinois at Chicago, 845 W. Taylor St., Chicago II 60607.; Hokkaido University, Sapporo 060, Japan.; Massachusetts Institute of Technology, Cambridge, MA 02139.

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