IDENTIFICATION OF THE $4P\sigma_{u} {^{1}\Pi_{u}}$ RYDBERG STATE OF $O_{2}$

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1995

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Ohio State University

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New high-resolution measurements of the $O_{2}$ photoabsorption cross section in the $1147 - 1155 {\AA}$ region are presented. The observation of three previously-unreported narrow lines in a band near $1148 {\AA}$ has enabled unambiguous assignment of the band to a $^{1}\Pi_{u} \leftarrow X^{3}{\Sigma^{-}}_{g}$ transition which gains strength through a spin-orbit interaction with the upper state of a $^{3}\Pi_{u} \leftarrow X^{3}{\Sigma^{-}}_{g}$ transition appearing at $1153 {\AA}$. Other lines in the $1148 {\AA}$ band are broadened by predissociation through a heterogeneous interaction with a nearly energetically coincident $^{1}\Delta_{u}$ level. The states, labelled $h^{1}\Pi_{u}, F^{3}\Pi_{u}$ and $i^{1}\Delta_{u}$, are predominantly of $4p\lambda$ Rydberg molecular orbital configurations although there are indications that the $\Pi_{u}$ states interact strongly with valence states of the same symmetry.

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Author Institution: The Australian National University, Canberra, ACT 0200, Australia.; University of Maryland, College Park, Maryland 20742, USA.

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