Probing the Cl-HCl complex via bond-specific photodissociation of (HCl)(2)

Infrared-ultraviolet double resonance has been used to photodissociate the free HCl bond of the HCl dimer. This creates Cl-HCl in a coherent superposi tion of electronic and vibrational states. Measurement of the translational energy of the departing H atom using high-n Rydberg time-of-flight spectro scopy enables the Cl-HCl potential surfaces to be probed. The features thus obtained agree with theoretical estimates. At long IR-UV delays, the faste st H atoms derive primarily from UV photodissociation of internally excited HCl (e.g., high rotational levels) formed by (HCl)(2) predissociation. (C) 1999 Elsevier Science B.V. All rights reserved.