Inter-Rydberg spectroscopy of argon and neon dimers

Kane, Daniel James

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https://hdl.handle.net/2142/19740 Copy

Description

Title

Inter-Rydberg spectroscopy of argon and neon dimers

Author(s)

Kane, Daniel James

Issue Date

1989

Doctoral Committee Chair(s)

Eden, James G.

Department of Study

Physics

Discipline

Physics

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Physics, Molecular

Language

eng

Abstract

Rydberg $\gets$ Rydberg transitions of Ar$\sb2$ and Ne$\sb2$ have been observed for the first time by laser-excitation spectroscopy. Molecular Rydbergs converging to the $A\sp2\Sigma\sbsp{1/2\rm u}{+}$ ion core having principal quantum numbers as large as 26 for Ar$\sb2$ and 17 for Ne$\sb2$ have been observed despite the predissociative nature of the high-lying Ar$\sb2$ and Ne$\sb2$ Rydbergs. The most prominent Rydberg series have been identified as the np$\pi\sb{\rm u}$ $\gets$ ms$\sigma\sb{\rm g}$ (Ar: m = 4, 5 $\leq$ n $\leq$ 26; Ne: m = 3, 4 $\leq$ n $\leq$ 17). The adiabatic ionization limits, relative to the lowest metastable state (4s$\sigma\sb{\rm g}$(1$\sb{\rm u}$, 0$\sbsp{\rm u}{-}$) for Ar$\sb2$, and 3s$\sigma\sb{\rm g}\sp3\Sigma\sbsp{\rm u}{+}$ for Ne$\sb2$), were also determined to be 29373 $\pm$ 2 cm$\sp{-1}$ for Ar$\sb2$ and 34399 $\pm$ 3 cm$\sp{-1}$ for Ne$\sb2$. The associated np$\pi\sb{\rm u}$ $\gets$ ms$\sigma\sb{\rm g}$ (v$\sp\prime$, v$\sp{\prime\prime}$) = (0, 1) Rydberg series has also been observed (Ar: m = 4, 5 $\leq$ n $\leq$ 10; Ne: m = 3, 4 $\leq$ n $\leq$ 7) with ionization limits of 29079 $\pm$ 5 cm$\sp{-1}$ for Ar$\sb2$ and 33870 $\pm$ 20 cm$\sp{-1}$ for Ne$\sb2$. Two more Rydberg series have been observed in Ar$\sb2$ and assigned to be the np$\sigma\sb{\rm u}$ and the nf$\pi\sb{\rm u}$ with the same series limit as the np$\pi\sb{\rm u}$ (29373 cm$\sp{-1}$). Also, several of the Rydberg $\gets$ Rydberg transitions in Ar$\sb2$ and Ne$\sb2$ have been rotationally resolved. This, to the knowledge of the author, is the first time any Rydberg $\gets$ Rydberg transitions have been rotationally resolved in the rare gas dimers heavier than He$\sb2$. Analysis of two of the bands indicate that B$\sb0$ $\simeq$ 0.17 cm$\sp{-1}$ for Ar$\sb2$4s$\sigma\sb{\rm g}$(1$\sb{\rm u}$, 0$\sbsp{\rm u}{-}$) and B$\sb0$ = 0.564 $\pm$ 0.007 cm$\sp{-1}$ for Ne$\sb2$3s$\sigma\sb{\rm g}\sp3\Sigma\sbsp{\rm u}{+}$. The photoionization cross section, as a function of wavelength, for the lowest metastable states have also been calculated from the data presented in this work.

Type of Resource

text

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http://hdl.handle.net/2142/19740

Copyright and License Information

Copyright 1989 Kane, Daniel James

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