Lifetimes of heavy-Rydberg ion-pair states formed through Rydberg electron transfer

The lifetimes of K(+)..Cl(-), K(+)..CN(-), and K(+)..SF(6)(-) heavy-Rydberg ion-pair states produced through Rydberg electron transfer reactions are measured directly as a function of binding energy using electric field induced detachment and the ion-pair decay channels discussed. The data are interpreted using a Monte Carlo collision code that models the detailed kinematics of electron transfer reactions. The lifetimes of K(+)..Cl(-) ion-pair states are observed to be very long, >100 micros, and independent of binding energy. The lifetimes of strongly bound (>30 meV) K(+)..CN(-) ion pairs are found to be similarly long but begin to decrease markedly as the binding energy is reduced below this value. This behavior is attributed to conversion of rotational energy in the CN(-) ion into translational energy of the ion pair. No long-lived K(+)..SF(6)(-) ion pairs are observed, their lifetimes decreasing with increasing binding energy. This behavior suggests that ion-pair loss is associated with mutual neutralization as a result of charge transfer.