期刊
JOURNAL OF CHEMICAL PHYSICS
卷 155, 期 24, 页码 -出版社
AIP Publishing
DOI: 10.1063/5.0070879
关键词
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资金
- National Science Foundation [CHE-1800410]
- AFOSR [FA9550-16-1-0117]
- National Science Foundation Graduate Research Fellowship Program [1122374]
- U.S. Department of Energy [DE-AC52-07NA27344]
This study investigates the vibrational autoionization dynamics of high-l Rydberg states using a long-range model for a simplified description. It explains the extensive angular momentum exchange between the ion-core and the Rydberg electron, as well as the dominant role of autoionization over predissociation in higher l states. The model also accurately predicts total decay rates and discusses potential applications in quantum state selection for molecular ion production.
In high orbital angular momentum (l & GE; 3) Rydberg states, the centrifugal barrier hinders the close approach of the Rydberg electron to the ion-core. As a result, these core-nonpenetrating Rydberg states can be well described by a simplified model in which the Rydberg electron is only weakly perturbed by the long-range electric properties (i.e., multipole moments and polarizabilities) of the ion-core. We have used a long-range model to describe the vibrational autoionization dynamics of high-l Rydberg states of nitric oxide (NO). In particular, our model explains the extensive angular momentum exchange between the ion-core and the Rydberg electron that had been previously observed in vibrational autoionization of f (l = 3) Rydberg states. These results shed light on a long-standing mechanistic question around these previous observations and support a direct, vibrational mechanism of autoionization over an indirect, predissociation-mediated mechanism. In addition, our model correctly predicts newly measured total decay rates of g (l = 4) Rydberg states because for l & GE; 4, the non-radiative 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.& nbsp;(C) 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
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