Abstract
The dissociative recombination of polyatomic molecular ions has been thought to normally be dominated by the crossing between a dissociative neutral surface and an ionic ground state surface. For some molecules such as H3+, however, the low energy dissociative recombination (DR) rate is observed to be high despite the absence of such a crossing. We show how the Jahn–Teller coupling mechanism can produce a surprisingly high DR rate in H3+ by first exciting a Rydberg state attached to an ionic vibrationally excited level, which subsequently dissociates. The resulting DR rate coefficients are in good agreement with storage ring experiments that have utilized a rotationally cold ionic target.
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