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Heavy Rydberg states: large amplitude vibrations

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Abstract

Extremely large vibrational amplitude (≈8700 a.u.) heavy Rydberg levels in the H[H with combining macron]1Σ+g state, located only 25 cm−1 below the ion-pair dissociation limit, are reported. The calculations are done using a hybrid log derivative/multichannel quantum defect approach that accounts for predissociation and is capable of dealing with any number of long-range closed channels, and of providing positions and widths for the heavy Rydberg resonances. In this case, resonance positions can be reproduced qualitatively using a simple diabatic model (however, the resonance widths cannot). Absolute quantum defects are derived for the vibrational series ranging from ν = 0 to ν = 2010. The influence of the Coulomb potential and continuity of heavy Rydberg behavior throughout the 1Σ+g manifold of states is demonstrated.

Graphical abstract: Heavy Rydberg states: large amplitude vibrations

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Publication details

The article was received on 21 May 2018, accepted on 21 Jun 2018 and first published on 21 Jun 2018


Article type: Paper
DOI: 10.1039/C8FD00096D
Citation: Faraday Discuss., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Heavy Rydberg states: large amplitude vibrations

    A. Kirrander, C. Jungen, R. J. Donovan and K. P. Lawley, Faraday Discuss., 2018, Advance Article , DOI: 10.1039/C8FD00096D

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