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Abstract

We have measured photoionization cross sections and photoelectron asymmetry parameters for each of the core levels of N₂O. We have also carried out frozen‐ and relaxed‐core Hartree–Fock studies of these cross sections so as to better understand the underlying shape resonant structure and the role of electronic relaxation in these processes. A broad shape resonance is observed in each of the core‐hole cross sections at 10‐20 eV kinetic energy and there is some evidence of a second shape resonance near the thresholds, an energy region which is not accessible experimentally. The cross sections also exhibit site‐specific behavior with maxima at widely separated photoelectron kinetic energies. These differences probably arise from the fact that photoelectron matrix elements for different core orbitals probe different regions of the shape resonant orbital which extends over the entire molecule. Although the higher energy shape resonances appear quite similar, Hartree–Fock studies show that the central nitrogen resonance is more sensitive to effects of electronic relaxation than the terminal nitrogen or oxygen resonances. Large differences are also seen between the photoelectron asymmetry parameters for the central and terminal atoms.