Abstract
Direct observation by time-resolved picosecond spectroscopy of the contact ion pair (CIP) allows the microdynamical rate constants for its (a) annihilation by internal return, (b) relaxation to the solvent-separated ion pair (SSIP), and (c) ionic exchange in the special salt effect to be quantitatively evaluated for the solvolysis mechanism (Scheme I) originally formulated by Winstein and co-workers. The relevant contact ion pair [Ar + ,T - ] is spontaneously generated by the 20-ps laser pulse excitation of the EDA complex from tetranitromethane (TNO 2 ) and anthracene (Ar)
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