Dynamics of Rydberg electron transfer to CH3CN: Velocity dependent studies (original) (raw)

The Journal of Chemical Physics, 2004

Abstract

The dynamics of free-ion production through electron transfer in K(np)/CH3CN collisions are examined through measurements using velocity-selected Rydberg atoms. The data show that Rydberg electron transfer leads to the creation of two groups of dipole-bound CH3CN− ions, one long lived (τ>85 μs), the other short lived (τ<1 μs). The velocity dependences associated with the production of both groups of ions are similar, the ion formation rate decreasing markedly with decreasing Rydberg atom velocity, principally as a consequence of postattachment electrostatic interactions between the product ions. The results are in reasonable accord with the predictions of a Monte Carlo collision model that considers the effect of crossings between the diabatic potential curves for the covalent K(np)/CH3CN system and the K+/CH3CN− ion pair. This model also accounts for the relatively small reaction rate constants, ∼0.5–1.0×10−8 cm3 s−1, associated with the formation of long-lived CH3CN− ions. N...

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