Doppler spectroscopy of chlorine atoms generated from photodissociation of hydrogen chloride and methyl chloride at 157 and 193 nm

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Abstract
Hydrogen chloride and methyl chloride are photodissociated at 193 and 157 nm. Branching ratios for production of the resulting chlorine atoms in the 2P1/2 state relative to the 2P3/2 state are determined to be 0.20±0.02 at 193 nm and 0.35±0.05 at 157 nm for HCl and 0.23±0.02 at 193 nm and 0.26±0.05 at 157 nm for CH3Cl. The Doppler profiles of the chlorine fragments have been measured and are interpreted by assuming their anisotropy parameters and translational energies. HCl undergoes a perpendicular optical transition at each of the two wavelengths. For CH3Cl, the transition is parallel at 193 nm and a mixture of parallel and perpendicular types at 157 nm.