Photoabsorption, photoionization, and Auger processes at the carbon K edge in CH3I

Ruaridh Forbes, Stephen T. Pratt, Alberto De Fanis, Aleksandar R. Milosavljević, Christophe Nicolas, John D. Bozek, Nicholas A. Besley, and David M. P. Holland
Phys. Rev. A 101, 023408 – Published 14 February 2020
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Abstract

The dynamics of photoabsorption, photoionization, and the associated Auger decay have been investigated at the carbon K edge in methyl iodide (CH3I) using linearly polarized synchrotron radiation. Ion yield measurements were used to investigate transitions in the pre-edge region due to excitations into either unoccupied valence or Rydberg states. The assignment of these transitions was achieved through comparison with theoretical x-ray absorption spectra calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation. Several of the Rydberg states belonging to series converging onto the C1s ionization limit exhibit significant vibrational structure that is also interpreted using theoretical calculations. The C1s in CH3I photoelectron spectrum was measured, and the observed vibrational structure was assigned with the aid of theoretical predictions. Polarization dependent, resonantly excited, valence shell photoelectron spectra were recorded at photon energies coinciding with the C1sσ*, C1s6sa1 and C1s6pe transitions in CH3I, thereby allowing photoelectron angular distributions to be determined. The nonresonantly excited C(KVV) Auger electron spectrum was measured and some of the features observed at high kinetic energies were attributed to transitions into valence orbitals possessing significant iodine character. The contributions of participator and spectator Auger decay to the resonantly excited photoelectron spectra have been assessed. The influence of participator decay appears minor whereas spectator decay results in the enhanced population of satellite states.

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  • Received 30 October 2019
  • Accepted 21 January 2020

DOI:https://doi.org/10.1103/PhysRevA.101.023408

©2020 American Physical Society

Physics Subject Headings (PhySH)

Atomic, Molecular & Optical

Authors & Affiliations

Ruaridh Forbes1,2, Stephen T. Pratt3, Alberto De Fanis4, Aleksandar R. Milosavljević5, Christophe Nicolas5, John D. Bozek5, Nicholas A. Besley6, and David M. P. Holland7,*

  • 1Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom
  • 2Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario, K1N 6N5 Canada
  • 3Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, USA
  • 4European XFEL GmbH, Holzkoppel 4, 22869 Schenefeld, Germany
  • 5Synchrotron SOLEIL, l’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France
  • 6School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom
  • 7Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD, United Kingdom

  • *david.holland@stfc.ac.uk

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Issue

Vol. 101, Iss. 2 — February 2020

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