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Title: An experimental and theoretical study of the C 1s ionization satellites in CH3I

Abstract

The C 1s ionization spectrum of CH3I has been studied both experimentally and theoretically. Synchrotron radiation has been employed to record polarization dependent photoelectron spectra at a photon energy of 614 eV. These spectra encompass the main-line due to the C 1s single-hole state and the peaks associated with the shake-up satellites. Vertical ionization energies and relative photoelectron intensities have been computed using the fourth-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function and the 6-311++G(**) basis set. The theoretical spectrum derived from these calculations agrees qualitatively with the experimental results, thereby allowing the principal spectral features to be assigned. According to our calculations, two (2)A(1) shake-up states of the C 1s(-1) sigma(CI) sigma CI* type with singlet and triplet intermediate coupling of the electron spins (S = 0, 1) play an important role in the spectrum and contribute significantly to the overall intensity. Both of these states are expected to have dissociative diabatic potential energy surfaces with respect to the C-I separation. Whereas the upper of these states perturbs the manifold of Rydberg states, the lower state forms a band which is characterized by a strongly increased width. Our results indicate that the lowest shake-up peak with significantmore » spectral intensity is due to the pair (S = 0, 1) of E-2 (C 1s(-1) I 5p sigma CI*) states. We predict that these E-2 states acquire photoelectron intensity due to spin-orbit interaction. Such interactions play an important role here due to the involvement of the I 5p orbitals.« less

Authors:
ORCiD logo [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]
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  1. Irkutsk State Univ. (Russia); Favorsky’s Institute of Chemistry, SB RAS, Irkutsk (Russia)
  2. Irkutsk State Univ. (Russia)
  3. Univ. College London, Bloomsbury (United Kingdom); Univ. of Ottawa, Ontario (Canada)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
  5. Daresbury Lab. (United Kingdom)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE; Ministry of Education and Science of the Russian Federation; Science and Technology Facilities Council
OSTI Identifier:
1546955
Alternate Identifier(s):
OSTI ID: 1525558; OSTI ID: 1559562
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Trofimov, A. B., Belogolova, A. M., Serebrennikova, S. A., Forbes, R., Pratt, S. T., and Holland, D. M. P. An experimental and theoretical study of the C 1s ionization satellites in CH3I. United States: N. p., 2019. Web. doi:10.1063/1.5099699.
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Trofimov, A. B., Belogolova, A. M., Serebrennikova, S. A., Forbes, R., Pratt, S. T., & Holland, D. M. P. An experimental and theoretical study of the C 1s ionization satellites in CH3I. United States. doi:10.1063/1.5099699.
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Trofimov, A. B., Belogolova, A. M., Serebrennikova, S. A., Forbes, R., Pratt, S. T., and Holland, D. M. P. Tue . "An experimental and theoretical study of the C 1s ionization satellites in CH3I". United States. doi:10.1063/1.5099699. https://www.osti.gov/servlets/purl/1546955.
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@article{osti_1546955,
title = {An experimental and theoretical study of the C 1s ionization satellites in CH3I},
author = {Trofimov, A. B. and Belogolova, A. M. and Serebrennikova, S. A. and Forbes, R. and Pratt, S. T. and Holland, D. M. P.},
abstractNote = {The C 1s ionization spectrum of CH3I has been studied both experimentally and theoretically. Synchrotron radiation has been employed to record polarization dependent photoelectron spectra at a photon energy of 614 eV. These spectra encompass the main-line due to the C 1s single-hole state and the peaks associated with the shake-up satellites. Vertical ionization energies and relative photoelectron intensities have been computed using the fourth-order algebraic-diagrammatic construction approximation scheme for the one-particle Green's function and the 6-311++G(**) basis set. The theoretical spectrum derived from these calculations agrees qualitatively with the experimental results, thereby allowing the principal spectral features to be assigned. According to our calculations, two (2)A(1) shake-up states of the C 1s(-1) sigma(CI) sigma CI* type with singlet and triplet intermediate coupling of the electron spins (S = 0, 1) play an important role in the spectrum and contribute significantly to the overall intensity. Both of these states are expected to have dissociative diabatic potential energy surfaces with respect to the C-I separation. Whereas the upper of these states perturbs the manifold of Rydberg states, the lower state forms a band which is characterized by a strongly increased width. Our results indicate that the lowest shake-up peak with significant spectral intensity is due to the pair (S = 0, 1) of E-2 (C 1s(-1) I 5p sigma CI*) states. We predict that these E-2 states acquire photoelectron intensity due to spin-orbit interaction. Such interactions play an important role here due to the involvement of the I 5p orbitals.},
doi = {10.1063/1.5099699},
journal = {Journal of Chemical Physics},
number = 22,
volume = 150,
place = {United States},
year = {2019},
month = {6}
}
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DOI:  10.1063/1.5099699
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