Abstract
In this paper we present new results on the photodissociation, geminate recombination, and vibrational relaxation of in various solvents. The photodissociation of involves localization of the excess charge on a recoiling I• photofragment. This charge again delocalizes as the I• and I− geminately recombine. The "charge flow" associated with recombination and subsequent large-amplitude vibrational motion is believed to greatly accelerate the vibrational relaxation of the nascent . Coupling of the charge flow with accepting solvent modes leads to relaxation rates which are extremely fast and non-exponential, even near the bottom of the potential well. These results are in stark contrast to similar experiments performed on neutral I2 which show nearly exponential vibrational relaxation rates that are an order of magnitude slower and are well-described by isolated binary interaction (IBC) theory.
© 1994 Optical Society of America
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