Abstract
The rotationally resolved, zero kinetic energy, pulsed-field ionization (ZEKE-PFI) spectrum of the HI+ X 2Π1/2, v+=0 level, obtained by double-resonance excitation via the HI F 1Δ2, v=0 level, is reported. The rotational and Λ-doubling constants for the HI+ X 2Π1/2, v+=0 level obtained from the experiment are close to those estimated theoretically by Mank et al. [J. Chem. Phys. 95, 1676 (1991)]. At higher pressures, the dissociative charge transfer reaction HI*+HI→HI++H+I− represents a potentially serious loss mechanism for the high Rydberg states that give rise to the ZEKE-PFI signal. This result is of more general applicability, because it provides evidence that collisions of the Rydberg electron with neighboring molecules can play a significant role in ZEKE-PFI experiments.
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