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Published September 1, 1993 | Published
Journal Article Open

Pulsed-field ionization threshold photoelectron spectroscopy with coherent extreme ultraviolet radiation: A comparison of CO and N_2

Abstract

Single‐photon zero‐kinetic‐energy pulsed‐field‐ionization spectra have been measured for the v^+=0 and 1 levels of CO^+ (X  ^2Σ^+) and the v^+=0 level of N_2^+ (X  ^2Σ_g^+) by coherent XUV radiation. In spite of similarities in the electronic structure of CO and N_2, the measured ion spectra show dramatically different intensities for the Q branches. These threshold spectra are interpreted on the basis of ab initio calculations of the ion rotational distributions. Agreement between the calculated and measured spectra is very encouraging. Improved values for the ionization potentials of CO (113 025.6 and 115 211.2±1.5 cm^(−1) for v^+=0 and 1, respectively) are reported and the unusual dynamics favoring ΔN<0 transitions are discussed. The CO spectra show quite different behavior for the ΔN<0 transitions for v^+=0 and v^+=1 bands, which is interpreted in terms of the relative importance of rotational autoionization in the two bands.

Additional Information

© 1993 American Institute of Physics. (Received 10 March 1993; accepted 10 May 1993) The experimental work done at Waterloo was supported by NSERC (Canada) and the Federal Networks of Centers of Excellence program, administered by NSERC. W. K. wishes to thank NSERC for a graduate scholarship. Work at the California Institute of Technology was supported by grants from the National Science Foundation, Air Force Office of Scientific Research, and the Office of Health and Environmental Research of the U. S. Department of Energy. We also acknowledge use of the resources of the Jet Propulsion Laboratory/California Institute of Technology CRAY Y-MP2E/116 supercomputer.

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August 20, 2023
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October 25, 2023