Abstract

Photofragment spectroscopy studies of the four heavier alkali chlorides at 266 nm are reported. Alkali atom recoil time-of-flight distributions provide indirect evidence for production of both ground 2P3/2 and excited 2P1/2 Cl atoms, but quantitative branching ratios are only approximate. The following bond dissociation energies (D00, kcal mole−1, all uncertainties ±2 kcal mole−1) are determined: NaCl=97.6; KCl=102.6; RbCl=101.3; CsCl=104.4. From recoil angular distributions the percentage parallel transition intensities to the unresolved excited states are calculated to be: NaCl=16±2; KCl=26±5; RbCl=32±1; CsCl=25±6.

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