4.6 Article

Auger electron angular distributions following excitation or ionization from the Xe 3d and F 1s levels in xenon difluoride

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 3, 页码 1367-1379

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp04797c

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  1. Science and Technology Facilities Council (United Kingdom)
  2. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC02-06CH11357, 20190046]

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Linearly polarized synchrotron radiation was used to record polarization dependent, non-resonant Auger electron spectra of XeF2, revealing the angular distribution characteristics and intrinsic anisotropy parameters of Auger electrons. Experimental results showed that the kinetic energy of electrons measured in resonantly excited spectra for a specific Auger transition is higher than that in directly ionized spectra.
Linearly polarized synchrotron radiation has been used to record polarization dependent, non-resonant Auger electron spectra of XeF2, encompassing the bands due to the xenon M45N1N45, M45N23N45, M45N45N45 and M45N45V and fluorine KVV transitions. Resonantly excited Auger spectra have been measured at photon energies coinciding with the Xe 3d(5/2) -> sigma* and the overlapped Xe 3d(3/2)/F 1s -> sigma* excitations in XeF2. The non-resonant and resonantly excited spectra have enabled the Auger electron angular distributions, as characterized by the beta(A) parameter, to be determined for the M45N45N45 transitions. In the photon energy range over which the Auger electron angular distributions were measured, theoretical results indicate that transitions into the epsilon f continuum channel dominate the Xe 3d photoionization in XeF2. In this limit, the theoretical value of the atomic alignment parameter (A(20)) characterizing the core ionized state becomes constant. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (alpha(2)) from the beta(A) parameters extracted from our non-resonant Auger spectra. For a particular Auger transition, the electron kinetic energy measured in the resonantly excited spectrum is higher than that in the directly ionized spectrum, due to the screening provided by the electron promoted into the sigma* orbital. The interpretation of the F KVV Auger band in XeF2 has been discussed in relation to previously published one-site populations of the doubly charged ions (XeF22+). The experimental results show that the ionization energies of the doubly charged states predominantly populated in the decay of a vacancy in the F 1s orbital in XeF2 tend to be higher than those populated in the decay of a vacancy in the Xe 4d level in XeF2.

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