Longrange model of vibrational autoionization in corenonpenetrating Rydberg states of NO
Abstract
In high orbital angular momentum ($\ell \geq 3$) Rydberg states, the centrifugal barrier hinders close approach of the Rydberg electron to the ioncore. As a result, these corenonpenetrating Rydberg states can be well described by a simplified model in which the Rydberg electron is only weakly perturbed by the longrange electric properties (i.e., multipole moments and polarizabilities) of the ioncore. We have used a longrange model to describe the vibrational autoionization dynamics of high$\ell$ Rydberg states of nitric oxide (NO). In particular, our model explains the extensive angular momentum exchange between the ioncore and Rydberg electron that had been previously observed in vibrational autoionization of $f$ ($\ell=3$) Rydberg states. These results shed light on a longstanding mechanistic question around these previous observations, and support a direct, vibrational mechanism of autoionization over an indirect, predissociationmediated mechanism. In addition, our model correctly predicts newly measured total decay rates of $g$ ($\ell=4$) Rydberg states because, for $\ell\geq4$, the nonradiative decay is dominated by autoionization rather than predissociation. We examine the predicted NO$^+$ ion rotational state distributions generated by vibrational autoionization of $g$ states and discuss applications of our model to achieve quantum state selection in the production of molecular ions.
 Publication:

arXiv eprints
 Pub Date:
 September 2021
 arXiv:
 arXiv:2109.04510
 Bibcode:
 2021arXiv210904510B
 Keywords:

 Physics  Atomic Physics;
 Physics  Chemical Physics
 EPrint:
 10 pages, 7 figures