Two-photon spectroscopy of Rydberg states of molecular oxygen

Journal Article · Mon Jan 01 04:00:00 EST 1990 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.458841· OSTI ID:6362050

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

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

Two-photon resonant, three-photon ionization spectrum of O₂ X ³Σ⁻_g, v"=0 is presented in the energy region between the 5s-4d complex and the O⁺₂ X ²Π_1/2g, v⁺=0 ionization threshold. The spectrum exhibits a number of new transitions to ns and nd Rydberg states with n=5-9 and v´=0 and 1 as well as transitions to the previously unobserved 5s-4d, v´=3 levels. For a given value of n and v´, the observed bands split into two groups separated by approximately the O⁺₂ X ²Π_1/2g --²Π_3/2g spin--orbit splitting. All of the bands show at least some sharp rotational structure, although in most cases this structure is limited to a few lines. In addition, the direct two-photon ionization spectrum of O₂ X ³Σ⁻_g, v"=0 is presented in the energy region between the O⁺₂ X ²Π_1/2g, v⁺=0 and 1 thresholds; the spectrum shows transitions to Rydberg states with n=8-12 and v´=1. These states are analogous to the v´=0 states observed below the ionization threshold, and they decay by vibrational autoionization into the v⁺=0 continuum. Taken together, the v´=0 and 1 Rydberg states observed here provide a significant addition to the knowledge of Rydberg series converging to the ground electronic state of O⁺₂.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE; Office of Energy Research (OER); Office of Health and Environmental Research (OHER)
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6362050
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Vol. 93:5; ISSN JCPSA; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
COUPLING
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
EXCITED STATES
INTERMEDIATE COUPLING
IONIZATION
L-S COUPLING
MULTI-PHOTON PROCESSES
NONMETALS
OXYGEN
PHOTOIONIZATION
RYDBERG STATES