Observation of l-dependent rate constants for ion production in Rydberg electron transfer reactions

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Abstract
Relative rate constants for negative ion production have been measured for the Rydberg electron transfer reactions Cs**(ns,np,nd) +SF6→Cs++SF−6 and Cs**(ns,np,nd) +CCl4→Cs++Cl−+CCl3. We find that rate constant for production of Cl− from CCl4 are dependent upon the angular momentum of the Rydberg electron, with knd>kns for values of n as large as 40. Preliminary measurements for potassium (ns,nd) Rydberg atoms show that the l dependence for K is much smaller than that for Cs. These results are inconsistent with the ‘‘free electron model’’ used to describe these reactions. It is suggested that the observed l dependence is related to postattachment interactions with the Rydberg atom core which affect the survival of the Cl− ions.