Abstract

The spontaneous predissociation of the B3Π(0+u) state of chlorine is discussed. Calculation of predissociation rate constants has been used to investigate the form of the repulsive potential which provides the dissociation channel. The calculations showed that the experimentally observed vibrational dependence of the predissociation rate cannot be accounted for by predissociation via the 1Π(1u) state. This is in contrast to the similar predissociations of the I2 and Br2B states, which are both predissociated by 1Π(1u) states.Further calculations demonstrate that the A3Π(1u) state provides the dissociative channel. Calculations were made utilizing an A-state potential-energy curve derived from spectroscopic data. Good quantitative agreement between the experimental and calculated predissociation rate constants was obtained.

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