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Title: Photoabsorption, Photoionization, and Auger Processes at the Carbon K-Edge in CH{sub 3}I

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 C1s -> sigma*, C1s -> 6sa(1) and C1s -> 6pe 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 spectramore » have been assessed. The influence of participator decay appears minor whereas spectator decay results in the enhanced population of satellite states.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC); United Kingdom Science and Technology Facilities Council; USDOE
OSTI Identifier:
1607442
Alternate Identifier(s):
OSTI ID: 1599682
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. A
Additional Journal Information:
Journal Volume: 101; Journal Issue: 2
Country of Publication:
United States
Language:
English

Citation Formats

Forbes, Ruaridh, Pratt, Stephen T., De Fanis, Alberto, Milosavljevic, Aleksandar R., Nicolas, Christophe, Bozek, John D., Besley, Nicholas A., and Holland, David M.P. Photoabsorption, Photoionization, and Auger Processes at the Carbon K-Edge in CH{sub 3}I. United States: N. p., 2020. Web. doi:10.1103/PhysRevA.101.023408.
Forbes, Ruaridh, Pratt, Stephen T., De Fanis, Alberto, Milosavljevic, Aleksandar R., Nicolas, Christophe, Bozek, John D., Besley, Nicholas A., & Holland, David M.P. Photoabsorption, Photoionization, and Auger Processes at the Carbon K-Edge in CH{sub 3}I. United States. doi:10.1103/PhysRevA.101.023408.
Forbes, Ruaridh, Pratt, Stephen T., De Fanis, Alberto, Milosavljevic, Aleksandar R., Nicolas, Christophe, Bozek, John D., Besley, Nicholas A., and Holland, David M.P. Fri . "Photoabsorption, Photoionization, and Auger Processes at the Carbon K-Edge in CH{sub 3}I". United States. doi:10.1103/PhysRevA.101.023408.
@article{osti_1607442,
title = {Photoabsorption, Photoionization, and Auger Processes at the Carbon K-Edge in CH{sub 3}I},
author = {Forbes, Ruaridh and Pratt, Stephen T. and De Fanis, Alberto and Milosavljevic, Aleksandar R. and Nicolas, Christophe and Bozek, John D. and Besley, Nicholas A. and Holland, David M.P.},
abstractNote = {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 C1s -> sigma*, C1s -> 6sa(1) and C1s -> 6pe 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.},
doi = {10.1103/PhysRevA.101.023408},
journal = {Physical Review. A},
number = 2,
volume = 101,
place = {United States},
year = {2020},
month = {2}
}

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