Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide

Auger electron spectra following excitation or ionization of the I 3d level in CH3I have been recorded with horizontally or vertically plane polarized synchrotron radiation. These spectra have enabled the Auger electron angular distributions, as characterized by the β parameter, to be determined. Th...

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Main Authors: Forbes, Ruaridh, De Fanis, Alberto, Bomme, Cédric, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Nandi, Saikat, Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D., Underwood, Jonathan G., Holland, David M.P.
Format: Article
Language:English
Published: AIP Publishing 2018
Online Access:https://eprints.nottingham.ac.uk/54975/
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author Forbes, Ruaridh
De Fanis, Alberto
Bomme, Cédric
Rolles, Daniel
Pratt, Stephen T.
Powis, Ivan
Besley, Nicholas A.
Nandi, Saikat
Milosavljević, Aleksandar R.
Nicolas, Christophe
Bozek, John D.
Underwood, Jonathan G.
Holland, David M.P.
author_facet Forbes, Ruaridh
De Fanis, Alberto
Bomme, Cédric
Rolles, Daniel
Pratt, Stephen T.
Powis, Ivan
Besley, Nicholas A.
Nandi, Saikat
Milosavljević, Aleksandar R.
Nicolas, Christophe
Bozek, John D.
Underwood, Jonathan G.
Holland, David M.P.
author_sort Forbes, Ruaridh
building Nottingham Research Data Repository
collection Online Access
description Auger electron spectra following excitation or ionization of the I 3d level in CH3I have been recorded with horizontally or vertically plane polarized synchrotron radiation. These spectra have enabled the Auger electron angular distributions, as characterized by the β parameter, to be determined. The I 3d photoionization partial cross section of CH3I has been calculated with the continuum multiple scattering approach, and the results show that in the photon energy range over which Auger spectra were measured, the I 3d cross section exhibits an atomic-like behavior and is dominated by transitions into the εf continuum channel. In this limit, the theoretical value of the alignment parameter (A20) characterizing the core ionized state in an atom becomes constant, independent of photon energy. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α2) from the β parameters extracted from our normal (non-resonant) molecular Auger spectra. The resulting anisotropy parameters for the M45N45N45 transitions in CH3I have been compared to those calculated for the corresponding transitions in xenon, and the experimental and theoretical results are in good agreement. Anisotropy parameters have also been measured for the M45N1N45, M45N23N45, and M45N45O23 transitions. For the M45N1N45 and M45N23N45 Auger decays in CH3I, the experimentally derived angular distributions do not exhibit the strong dependence on the final ionic state that is predicted for these transitions in xenon. Resonantly excited Auger spectra have been recorded at 620.4 and 632.0 eV, coinciding with the I 3d5/2 → σ* and 3d3/2 → σ* transitions, respectively. The resulting Auger electron angular distributions for the M4N45N45 and M5N45N45 decays were found to exhibit a higher anisotropy than those for the normal process. This is due to the larger photo-induced alignment in the neutral core excited state. For a particular Auger transition, the Auger electron kinetic energy measured in the resonantly excited spectrum is higher than that in the normal spectrum. This shift, due to the screening provided by the electron excited into the σ* orbital, has been rationalized by calculating orbital ionization energies of I 3d excited and I 3d ionized states in CH3I.
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spelling nottingham-549752018-09-14T13:38:17Z https://eprints.nottingham.ac.uk/54975/ Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide Forbes, Ruaridh De Fanis, Alberto Bomme, Cédric Rolles, Daniel Pratt, Stephen T. Powis, Ivan Besley, Nicholas A. Nandi, Saikat Milosavljević, Aleksandar R. Nicolas, Christophe Bozek, John D. Underwood, Jonathan G. Holland, David M.P. Auger electron spectra following excitation or ionization of the I 3d level in CH3I have been recorded with horizontally or vertically plane polarized synchrotron radiation. These spectra have enabled the Auger electron angular distributions, as characterized by the β parameter, to be determined. The I 3d photoionization partial cross section of CH3I has been calculated with the continuum multiple scattering approach, and the results show that in the photon energy range over which Auger spectra were measured, the I 3d cross section exhibits an atomic-like behavior and is dominated by transitions into the εf continuum channel. In this limit, the theoretical value of the alignment parameter (A20) characterizing the core ionized state in an atom becomes constant, independent of photon energy. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α2) from the β parameters extracted from our normal (non-resonant) molecular Auger spectra. The resulting anisotropy parameters for the M45N45N45 transitions in CH3I have been compared to those calculated for the corresponding transitions in xenon, and the experimental and theoretical results are in good agreement. Anisotropy parameters have also been measured for the M45N1N45, M45N23N45, and M45N45O23 transitions. For the M45N1N45 and M45N23N45 Auger decays in CH3I, the experimentally derived angular distributions do not exhibit the strong dependence on the final ionic state that is predicted for these transitions in xenon. Resonantly excited Auger spectra have been recorded at 620.4 and 632.0 eV, coinciding with the I 3d5/2 → σ* and 3d3/2 → σ* transitions, respectively. The resulting Auger electron angular distributions for the M4N45N45 and M5N45N45 decays were found to exhibit a higher anisotropy than those for the normal process. This is due to the larger photo-induced alignment in the neutral core excited state. For a particular Auger transition, the Auger electron kinetic energy measured in the resonantly excited spectrum is higher than that in the normal spectrum. This shift, due to the screening provided by the electron excited into the σ* orbital, has been rationalized by calculating orbital ionization energies of I 3d excited and I 3d ionized states in CH3I. AIP Publishing 2018-09-06 Article PeerReviewed application/pdf en https://eprints.nottingham.ac.uk/54975/1/Methyliodide_v47.pdf Forbes, Ruaridh, De Fanis, Alberto, Bomme, Cédric, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Nandi, Saikat, Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D., Underwood, Jonathan G. and Holland, David M.P. (2018) Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide. The Journal of Chemical Physics, 149 (9). 094304. ISSN 0021-9606 https://aip.scitation.org/doi/10.1063/1.5045640 doi:10.1063/1.5045640 doi:10.1063/1.5045640
spellingShingle Forbes, Ruaridh
De Fanis, Alberto
Bomme, Cédric
Rolles, Daniel
Pratt, Stephen T.
Powis, Ivan
Besley, Nicholas A.
Nandi, Saikat
Milosavljević, Aleksandar R.
Nicolas, Christophe
Bozek, John D.
Underwood, Jonathan G.
Holland, David M.P.
Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title_full Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title_fullStr Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title_full_unstemmed Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title_short Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
title_sort auger electron angular distributions following excitation or ionization of the i 3d level in methyl iodide
url https://eprints.nottingham.ac.uk/54975/
https://eprints.nottingham.ac.uk/54975/
https://eprints.nottingham.ac.uk/54975/