Very strong Rydberg atom scattering in K(12p)–CH3NO2 collisions: Role of transient ion pair formation

Collisions between K(12p) Rydberg atoms and CH3NO2 target molecules are studied. Whereas CH3NO2 can form long-lived valence-bound CH3NO2− ions, the data provide no evidence for production of long-lived K+⋯CH3NO2− ion pair states. Rather, the data show that collisions result in unusually strong Rydberg atom scattering. This behavior is attributed to ion-ion scattering resulting from formation of transient ion pair states through transitions between the covalent K(12p) + CH3NO2 and ionic K+ + (dipole bound) CH3NO2− terms in the quasimolecule formed during collisions. The ion-pair states are destroyed through rapid dissociation of the CH3NO2− ions induced by the field of the K+ core ion, the detached electron remaining bound to the K+ ion in a Rydberg state. Analysis of the experimental data shows that ion pair lifetimes ≳10 ps are sufficient to account for the present observations. The present results are consistent with recent theoretical predictions that Rydberg collisions with CH3NO2 will result in stron...

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