Long-range model of vibrational autoionization in core-nonpenetrating Rydberg states of NO

Barnum, Timothy J.; Clausen, Gloria; Jiang, Jun; Coy, Stephen L.; Field, Robert W.

doi:10.1063/5.0070879

Long-range model of vibrational autoionization in core-nonpenetrating Rydberg states of NO

Journal Article · Mon Dec 27 00:00:00 EST 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0070879· OSTI ID:1845201

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Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
ETH Zürich (Switzerland)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

In high orbital angular momentum (ℓ ≥ 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 ≥ 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1845201

Alternate ID(s):: OSTI ID: 1837462

Report Number(s):: LLNL-JRNL-827806; 1040643

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Long-range model of vibrational autoionization in core-nonpenetrating Rydberg states of NO

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