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Title: Dynamics of Rydberg electron transfer to CH{sub 3}CN: Velocity dependent studies

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1795651· OSTI ID:20658011
; ; ;  [1]
  1. Department of Physics and Astronomy and the Rice Quantum Institute, Rice University, Houston, Texas 77005-1892 (United States)

The dynamics of free-ion production through electron transfer in K(np)/CH{sub 3}CN 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 CH{sub 3}CN{sup -} ions, one long lived ({tau}>85 {mu}s), the other short lived ({tau}<1 {mu}s). 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)/CH{sub 3}CN system and the K{sup +}/CH{sub 3}CN{sup -} ion pair. This model also accounts for the relatively small reaction rate constants, {approx}0.5-1.0x10{sup -8} cm{sup 3} s{sup -1}, associated with the formation of long-lived CH{sub 3}CN{sup -} ions. No velocity dependence in the lifetime of the CH{sub 3}CN{sup -} ions is observed.

OSTI ID:
20658011
Journal Information:
Journal of Chemical Physics, Vol. 121, Issue 15; Other Information: DOI: 10.1063/1.1795651; (c) 2004 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English