skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
+ Show Author Affiliations
  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). Chemical Sciences, Geosciences, and Biosciences Division; 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. https://doi.org/10.1063/1.5099699.
Copy to clipboard
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. https://doi.org/10.1063/1.5099699
Copy to clipboard
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. https://doi.org/10.1063/1.5099699. https://www.osti.gov/servlets/purl/1546955.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5099699
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Theory of X-Ray Satellites
journal, April 1967

Observation of correlation effects in zero kinetic energy electron spectra near the N1 s and C1 s thresholds in N 2 , CO, C 6 H 6 , and C 2 H 4
journal, November 1988

  • Medhurst, L. J.; Ferrett, T. A.; Heimann, P. A.
  • The Journal of Chemical Physics, Vol. 89, Issue 10
  • DOI: 10.1063/1.455425

Near-threshold behavior of the K -shell satellites in CO
journal, June 1994

Inner-shell single and double ionization potentials of aminophenol isomers
journal, August 2011

  • Kryzhevoi, Nikolai V.; Santra, Robin; Cederbaum, Lorenz S.
  • The Journal of Chemical Physics, Vol. 135, Issue 8
  • DOI: 10.1063/1.3624393

Threshold phenomena in high-resolution core-level photoelectron spectroscopy: the ethene molecule
journal, June 1998

  • Kempgens, B.; Kivimäki, A.; Itchkawitz, B. S.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 93, Issue 1-3
  • DOI: 10.1016/s0368-2048(98)00156-x

Symmetry-Resolved Vibrational Spectra of Carbon K -Shell Photoelectron Satellites in Carbon Monoxides: Experiment and Theory
journal, June 2005

Photoionization of atoms using synchrotron radiation
journal, September 1992

Symmetry-dependent vibrational excitation in N 1s photoionization of N2: Experiment and theory
journal, March 2006

  • Ehara, M.; Nakatsuji, H.; Matsumoto, M.
  • The Journal of Chemical Physics, Vol. 124, Issue 12
  • DOI: 10.1063/1.2181144

Valence shell excitation accompanying photoionization in mercury
journal, October 1974

  • Berkowitz, J.; Dehmer, J. L.; Kim, Y. ‐K.
  • The Journal of Chemical Physics, Vol. 61, Issue 7
  • DOI: 10.1063/1.1682379

The ultraviolet absorption cross sections of CH3I temperature dependent gas and liquid phase measurements
journal, August 1995

Charge transfer effects in molecule–negative ion complexes induced by core ionization
journal, August 2003

  • Streltsov, A. I.; Dobrodey, N. V.; Cederbaum, L. S.
  • The Journal of Chemical Physics, Vol. 119, Issue 6
  • DOI: 10.1063/1.1589002

Theoretical C1s and O1s core shake-up spectra of CO by highly correlated QDPTCI approach
journal, November 1999

  • Fronzoni, G.; Alti, G. De; Decleva, P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 32, Issue 22
  • DOI: 10.1088/0953-4075/32/22/313

New approach to the one-particle Green's function for finite Fermi systems
journal, September 1983

High resolution O 1s photoelectron shake-up satellite spectrum of H2O
journal, April 2006

On Green’s function calculations of the static self‐energy part, the ground state energy and expectation values
journal, August 1989

  • Schirmer, J.; Angonoa, G.
  • The Journal of Chemical Physics, Vol. 91, Issue 3
  • DOI: 10.1063/1.457081

VUV spectroscopy of CH3Cl and CH3I
journal, January 2007

C 1s and O 1s photoelectron spectra of formaldehyde with satellites: theory and experiment
journal, March 2005

  • Kuramoto, K.; Ehara, M.; Nakatsuji, H.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 142, Issue 3
  • DOI: 10.1016/j.elspec.2004.09.011

Extension of Gaussian‐2 (G2) theory to bromine‐ and iodine‐containing molecules: Use of effective core potentials
journal, August 1995

  • Glukhovtsev, Mikhail N.; Pross, Addy; McGrath, Mark P.
  • The Journal of Chemical Physics, Vol. 103, Issue 5
  • DOI: 10.1063/1.469712

Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
journal, September 2018

  • Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cédric
  • The Journal of Chemical Physics, Vol. 149, Issue 9
  • DOI: 10.1063/1.5045640

The vibrational structure of a conjugate shake-up satellite band in the C 1s core-level photoemission of CO
journal, May 2007

Relaxation effects in C1s photoionisation of CO: a high resolution photoelectron study in the near-threshold region
journal, December 1995

  • Köppe, H. M.; Kilcoyne, A. L. D.; Feldhaus, J.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 75
  • DOI: 10.1016/0368-2048(95)02391-7

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Recent progress in ESCA studies of gases
journal, January 1974

Strong charge-transfer effects in the Mg 2 p − 1 core-level spectrum of MgB 2
journal, October 2002

Angular distributions of the C(1s) photoelectron satellites in CO
journal, November 1995

  • Hemmers, O.; Whitfield, S. B.; Berrah, N.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 28, Issue 22
  • DOI: 10.1088/0953-4075/28/22/003

Strong interatomic effects accompanying core ionization of atomic clusters
journal, January 2002

X-ray Spectroscopy of Heterocyclic Biochemicals: Xanthine, Hypoxanthine, and Caffeine
journal, June 2012

  • Plekan, Oksana; Feyer, Vitaliy; Richter, Robert
  • The Journal of Physical Chemistry A, Vol. 116, Issue 23
  • DOI: 10.1021/jp300459p

Inner shell excitation of CH 3F, CH 3Cl, CH 3Br and CH 3I by 2.5 keV electron impact
journal, January 1978

Satellite intensities in the K -shell photoionization of CO
journal, November 1991

Spin–orbit effects, electronic decay and breakdown phenomena in the photoelectron spectra of iodomethane
journal, October 2012

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955

  • Mulliken, R. S.
  • The Journal of Chemical Physics, Vol. 23, Issue 10
  • DOI: 10.1063/1.1740588

An intermediate state representation approach to K-shell ionization in molecules. II. Computational tests
journal, July 2003

  • Thiel, Alexander; Schirmer, Jochen; Köppel, Horst
  • The Journal of Chemical Physics, Vol. 119, Issue 4
  • DOI: 10.1063/1.1584658

Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide
journal, October 2018

  • Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cédric
  • The Journal of Chemical Physics, Vol. 149, Issue 14
  • DOI: 10.1063/1.5035496

High-resolution C 1 s photoelectron spectra of methane
journal, June 1996

  • Köppe, H. M.; Itchkawitz, B. S.; Kilcoyne, A. L. D.
  • Physical Review A, Vol. 53, Issue 6
  • DOI: 10.1103/physreva.53.4120

On the core-hole photoelectron satellites in N2 and CO
journal, September 1987

  • Schirmer, J.; Angonoa, G.; Cederbaum, L. S.
  • Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 5, Issue 3
  • DOI: 10.1007/bf01436930

A study of the photoionisation dynamics of chloromethane and iodomethane
journal, August 2006

Theoretical K ‐shell ionization spectra of N 2 and CO by a fourth‐order Green’s function method
journal, December 1987

  • Angonoa, G.; Walter, O.; Schirmer, J.
  • The Journal of Chemical Physics, Vol. 87, Issue 12
  • DOI: 10.1063/1.453424

A comprehensive photoabsorption, photoionization, and shake-up excitation study of the C 1s cross section of benzene
journal, November 2000

  • Rennie, E. E.; Kempgens, B.; Köppe, H. M.
  • The Journal of Chemical Physics, Vol. 113, Issue 17
  • DOI: 10.1063/1.1290029

Near-Threshold Measurements of the C   1 s Satellites in the Photoelectron Spectrum of CO
journal, October 1986

Resolution and signal‐to‐background enhancement in gas‐phase electron spectroscopy
journal, August 1993

  • Baltzer, P.; Karlsson, L.; Lundqvist, M.
  • Review of Scientific Instruments, Vol. 64, Issue 8
  • DOI: 10.1063/1.1143957

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

Multiconfiguration multichannel Schwinger study of the C(1 s ) photoionization of CO including shake-up satellites
journal, March 1993

C1s and O1s photoelectron satellite spectra of CO with symmetry-dependent vibrational excitations
journal, September 2006

  • Ehara, M.; Kuramoto, K.; Nakatsuji, H.
  • The Journal of Chemical Physics, Vol. 125, Issue 11
  • DOI: 10.1063/1.2346683

Vibrationally resolved threshold photoemission of N2 and CO at the N and C K-edges
journal, June 1992

A method to determine a transmission correction for electron spectrometers using synchrotron radiation
journal, October 1994

  • Jauhiainen, J.; Ausmees, A.; Kivimäkia, A.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 69, Issue 3
  • DOI: 10.1016/0368-2048(94)02197-8

Many-body theory of core holes
journal, July 1980

Vibrational and Vibronic Structure in the Valence Electron Spectra of CH 3 X Molecules (X=F, Cl, Br, I, OH)
journal, November 1977

Vibrational and shake-up excitations in the C 1s photoionization of ethane and deuterated ethane
journal, January 1999

  • Rennie, E. E.; Köppe, H. M.; Kempgens, B.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 32, Issue 11
  • DOI: 10.1088/0953-4075/32/11/316

An analysis of configuration-interaction model spaces for the study of the core photoelectron spectra of small molecules
journal, November 1988

  • Lisini, A.; Fronzoni, G.; Decleva, P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 21, Issue 22
  • DOI: 10.1088/0953-4075/21/22/005

Threshold Behaviour and Resonances in the Photoionization of Atoms and Molecules
journal, January 1990

Theory of core‐level photoemission correlation state spectra
journal, May 1976

  • Martin, R. L.; Shirley, D. A.
  • The Journal of Chemical Physics, Vol. 64, Issue 9
  • DOI: 10.1063/1.432679

The influence of the bromine atom Cooper minimum on the photoelectron angular distributions and branching ratios of the four outermost bands of bromobenzene
journal, October 2015

  • Powis, I.; Holland, D. M. P.; Antonsson, E.
  • The Journal of Chemical Physics, Vol. 143, Issue 14
  • DOI: 10.1063/1.4931642

Photon energy dependence of the high resolution C 1 s photoelectron spectrum of CO in the threshold region
journal, August 1993

Description of two- and many-electron processes by the SAC-CI method
journal, February 1991

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983

  • Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W.
  • Journal of Computational Chemistry, Vol. 4, Issue 3
  • DOI: 10.1002/jcc.540040303

Foreign and native coordination effects in core-level spectra of mixed Be-Mg clusters
journal, August 2002

  • Dobrodey, N. V.; Streltsov, A. I.; Cederbaum, L. S.
  • The Journal of Chemical Physics, Vol. 117, Issue 8
  • DOI: 10.1063/1.1501128

One-electron versus multielectron effects in the near-threshold C 1s photoionization of acetylene
journal, September 1997

  • Kempgens, B.; Kivimäki, A.; Köppe, H. M.
  • The Journal of Chemical Physics, Vol. 107, Issue 11
  • DOI: 10.1063/1.474796

Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide
text, January 2018

  • Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cedric
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2019-00088

Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
text, January 2018

  • Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cedric
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2019-00089
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Intermediate state representation approach to physical properties of molecular electron-detached states. I. Theory and implementation
    journal, January 2020

    • Dempwolff, Adrian L.; Paul, Alexander C.; Belogolova, Alexandra M.
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5137792
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: