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Volume 13: Pages 290-296, 2000

Valence‐Shell Autoionization of NO

S. H. Southworth ¹, T. A. Ferrett ², J. E. Hardis ³, A. C. Parr ³, J. L. Dehmer ⁴

¹Argonne National Laboratory, Argonne, Illinois 60439 U.S.A.

²Carleton College, Northfield, Minnesota 55057 U.S.A.

³National Institute of Standards and Technology, Gaithersburg, Maryland 20899 U.S.A.

⁴National Science Foundation, Arlington, Virginia 22230 U.S.A.

Autoionization of valence and Rydberg states in NO over the 12.5–18 eV photon energy range was studied by vibrationally resolved photoelectron spectroscopy of the 2 π orbital. Complex, oscillatory structure is observed in NO⁺ (2π⁻¹) X¹Σ⁺ partial cross sections, branching ratios, and photoelectron anisotropy parameters due to autoionizing valence states and Rydberg states associated with the 1 π⁻¹ and 5 σ⁻¹ channels. Autoionization of the 5 σ → np(π, σ) (υ′ = 0), n = 3–5 Rydberg states leading to the (5 σ⁻¹) b³ Πstate of NO⁺ produces very high vibrational levels of (2 π⁻¹) X¹Σ⁺. Autoionization of the 5 σ → 3p π (υ′ = 0) Rydberg state was characterized by resonance profiles of photoelectron cross sections and angular distributions.

Keywords: molecular autoionization, photoelectron spectroscopy, synchrotron radiation

Received: June 19, 2000; Published online: December 15, 2008