Systematics of Rydberg structure in the spectra of the rare gas dimers between the atomic ²P⁰_3/2 and ²P⁰_1/2 fine-structure thresholds

Journal Article · Thu Jan 01 04:00:00 EST 1981 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.441965· OSTI ID:5945151

Dehmer, Patricia M. ^[1]; Pratt, Stephen T. ^[1]

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1. Argonne National Lab. (ANL), Argonne, IL (United States)

The relative photoionization cross sections for the rare gas dimers Ar₂, Kr₂, and Xe₂ were measured in the energy region between the respective atomic ²P_3/2⁰ and ²P_1/2⁰ fine-structure thresholds at wavelength resolutions of 0.15 Â for Ar₂, 0.28 Â for Kr₂, and 0.45 Â for Xe₂. Discrete autoionization structure was observed for all three systems and has been partially analyzed in terms of Rydberg series converging to the C ²Π_1/2u state of the molecular ions. Vertical binding energies for the individual Rydberg states were estimated based on the assumption that the Rydberg states dissociate to a rare gas atom in an ns'[1/2]₁⁰ or nd'[3/2]₁⁰ excited state plus a rare gas atom in the ¹S₀ ground state. The binding energies thus obtained are in excellent agreement with the corresponding values for the C ²Π_1/2u ionic states obtained from previously reported photoelectron spectra. Some of the molecular structure exhibits Beutler--Fano profiles similar to those observed in the nd'[3/2]₁⁰ atomic series. This is in contrast to the energy region near the first ionization threshold, where it is extremely difficult to find a simple correlation between the atomic and molecular Rydberg structure.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE
• OSTI ID: 5945151
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 75; ISSN JCPSA6; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
ARGON
AUTOIONIZATION
BINDING ENERGY
CROSS SECTIONS
DIMERS
ELEMENTS
ENERGY
FINE STRUCTURE
FLUIDS
GASES
IONIZATION
KRYPTON
NONMETALS
PHOTOIONIZATION
RARE GASES
SPECTRA
XENON