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The Role of Rydberg States in Spectroscopy and Photochemistry pp 249–265Cite as

From Rydbergs To Zeke States

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Part of the book series: Understanding Chemical Reactivity ((UCRE,volume 20))

Summary

The observation of very long lived Rydberg type states was an unanticipated effect. These states live a thousand fold longer than predicted, but exist not only in a very narrow band of a few cm −1 below the IP of the molecule, but, since each ro/vibrational state of the ion is also the convergence limit of a Rydberg series, each of these states also has such a narrow band of long lived states. These highly stable states are not the optically accessible Rydberg states, but rather are dark states that have been produced from these optically active states by conversion of the electrons to near circular orbits as the result of symmetry breakings due to external fields, either applied or inherent, or due to ions in the vicinity. These new states lead to electrons produced near threshold with virtually no kinetic energy, hence they are termed ZEKE states.

The long lived property of these neutral ZEKE states makes them easy to separate from all other species. After such separation they can be readily detected by ionization with stronger fields. This forms the basis of a new, extremely high resolution and accurate spectroscopy of molecular ions, limited only by laser resolution. It is a facile technique and as such it has many advantages for ion spectroscopy - and indirectly for neutral species.

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Authors and Affiliations

  1. Institut für Physikalische und Theoretische Chemie, Technische Universität München, 5747, Garching, Germany

    Andrew Held & Edward W. Schlag

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  1. Andrew Held
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Editors and Affiliations

  1. Dèpartement de Chimie, Universitè de Montrèal, Quèbec, Canada

    C. Sándorfy

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© 1999 Kluwer Academic Publishers

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Held, A., Schlag, E.W. (1999). From Rydbergs To Zeke States. In: Sándorfy, C. (eds) The Role of Rydberg States in Spectroscopy and Photochemistry. Understanding Chemical Reactivity, vol 20. Springer, Dordrecht. https://doi.org/10.1007/0-306-46938-3_9

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  • DOI: https://doi.org/10.1007/0-306-46938-3_9

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-5533-5

  • Online ISBN: 978-0-306-46938-1

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