Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide
Abstract
Ionization of the I 3d, 4s, and 4p orbitals in methyl iodide (CH3I) has been studied by using synchrotron radiation to measure the total ion yield and by recording photoelectron spectra with linearly polarized radiation in two polarization orientations. The complete photoelectron spectrum of CH3I has been recorded at several photon energies, and bands due to the C 1s, I 3d, 4s, 4p, and 4d atomic-like orbitals, as well as the molecular orbitals, have been observed and assigned. In the vicinity of the I 3d5/2 and 3d3/2 ionization thresholds at 626.8 and 638.3 eV, respectively, the ion yield displays weak structure in the pre-edge region due to transitions into valence or Rydberg states, and, at higher energies, a shoulder and a broad maximum attributed to the I 3d5/2 → εf and the I 3d3/2 → εf shape resonances, respectively. The absorption spectrum calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation, has allowed assignments to be proposed for the valence and Rydberg states. The Stieltjes imaging technique has been used to simulate the absorption spectrum above the ionization threshold and indicates that transitions into the f(l = 3) continuum channel dominate. This conclusion has been corroborated by a Continuummore »
- Authors:
-
- Univ. College London, London (United Kingdom). Dept. of Physics and Astronomy; Univ. of Ottawa, Ottawa, ON (Canada). Dept. of Physics
- European X-ray Free-Electron Laser (XFEL), Hamburg (Germany)
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
- Kansas State Univ., Manhattan, KS (United States). J. R. Macdonald Lab., Dept. of Physics
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
- Univ. of Nottingham (United Kingdom). School of Chemistry
- National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France)
- Synchrotron SOLEIL, Paris (France)
- Univ. College London, London (United Kingdom). Dept. of Physics and Astronomy
- Daresbury Lab. (United Kingdom).
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Science and Technology Facilities Council (STFC) (United Kingdom)
- OSTI Identifier:
- 1487114
- Alternate Identifier(s):
- OSTI ID: 1476694
- Grant/Contract Number:
- AC02-06CH11357; FG02-86ER13491
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 149; Journal Issue: 14; 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
Citation Formats
Forbes, Ruaridh, De Fanis, Alberto, Bomme, Cédric, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Simon, Marc, Nandi, Saikat, Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D., Underwood, Jonathan G., and Holland, David M. P. Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide. United States: N. p., 2018.
Web. doi:10.1063/1.5035496.
Forbes, Ruaridh, De Fanis, Alberto, Bomme, Cédric, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Simon, Marc, Nandi, Saikat, Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D., Underwood, Jonathan G., & Holland, David M. P. Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide. United States. https://doi.org/10.1063/1.5035496
Forbes, Ruaridh, De Fanis, Alberto, Bomme, Cédric, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Simon, Marc, Nandi, Saikat, Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D., Underwood, Jonathan G., and Holland, David M. P. Sun .
"Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide". United States. https://doi.org/10.1063/1.5035496. https://www.osti.gov/servlets/purl/1487114.
@article{osti_1487114,
title = {Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide},
author = {Forbes, Ruaridh and De Fanis, Alberto and Bomme, Cédric and Rolles, Daniel and Pratt, Stephen T. and Powis, Ivan and Besley, Nicholas A. and Simon, Marc and Nandi, Saikat and Milosavljević, Aleksandar R. and Nicolas, Christophe and Bozek, John D. and Underwood, Jonathan G. and Holland, David M. P.},
abstractNote = {Ionization of the I 3d, 4s, and 4p orbitals in methyl iodide (CH3I) has been studied by using synchrotron radiation to measure the total ion yield and by recording photoelectron spectra with linearly polarized radiation in two polarization orientations. The complete photoelectron spectrum of CH3I has been recorded at several photon energies, and bands due to the C 1s, I 3d, 4s, 4p, and 4d atomic-like orbitals, as well as the molecular orbitals, have been observed and assigned. In the vicinity of the I 3d5/2 and 3d3/2 ionization thresholds at 626.8 and 638.3 eV, respectively, the ion yield displays weak structure in the pre-edge region due to transitions into valence or Rydberg states, and, at higher energies, a shoulder and a broad maximum attributed to the I 3d5/2 → εf and the I 3d3/2 → εf shape resonances, respectively. The absorption spectrum calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation, has allowed assignments to be proposed for the valence and Rydberg states. The Stieltjes imaging technique has been used to simulate the absorption spectrum above the ionization threshold and indicates that transitions into the f(l = 3) continuum channel dominate. This conclusion has been corroborated by a Continuum Multiple Scattering–Xα (CMS–Xα) calculation. The asymmetric broadening of the photoelectron bands associated with the I 3d orbital, due to post collision interaction, is taken into account in our experimental analysis. Experimentally derived photoelectron anisotropy parameters for the I 3d orbital are in good agreement with the theoretical predictions obtained with the CMS–Xα approach. The I 3d shake-up/shake-off photoelectron spectrum has been recorded, and assignments have been proposed for several of the satellites. The M4N45N45 and M5N45N45 Auger electron yields have been measured, and that for the M5N45N45 decay exhibits a maximum due to interchannel coupling between the 3d5/2 and 3d3/2 continua. The photoelectron band associated with the I 4p orbital has an unusual appearance. Based upon previous theoretical work for the analogous Xe 4p orbital, it appears that the initial I 4p-1 hole state decays rapidly through Coster-Kronig and super-Coster-Kronig transitions. This leads to a redistribution of the spectral intensity associated with the I 4p orbital and results in a photoelectron spectrum containing a single structured band together with an extended continuum. Another continuum is observed on the high binding energy side of the peak due to the 4s orbital, and we assign this to super-Coster-Kronig transitions into the 4p-14d-1 continuum.},
doi = {10.1063/1.5035496},
journal = {Journal of Chemical Physics},
number = 14,
volume = 149,
place = {United States},
year = {Sun Oct 14 00:00:00 EDT 2018},
month = {Sun Oct 14 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Electron distribution in the xenon fluorides and xenon oxide tetrafluoride by ESCA and evidence for orbital independence in the xenon-fluorine bonding
journal, April 1974
- Carroll, T. X.; Shaw, R. W.; Thomas, T. D.
- Journal of the American Chemical Society, Vol. 96, Issue 7
Newly Observed Structure in the Photoionization Continua of Kr and Xe below 160 Å
journal, January 1965
- Codling, K.; Madden, R. P.
- Applied Optics, Vol. 4, Issue 11
3d photoabsorption in gaseous and solid xenon
journal, January 1983
- Yagci, O.; Wilson, J. E.
- Journal of Physics C: Solid State Physics, Vol. 16, Issue 2
Inner-shell photoionization and core-hole decay of Xe and XeF2
journal, June 2015
- Southworth, Stephen H.; Wehlitz, Ralf; Picón, Antonio
- The Journal of Chemical Physics, Vol. 142, Issue 22
Angular Distribution of Photoelectrons
journal, January 1968
- Cooper, J.; Zare, R. N.
- The Journal of Chemical Physics, Vol. 48, Issue 2
Photoionization of atoms using synchrotron radiation
journal, September 1992
- Schmidt, V.
- Reports on Progress in Physics, Vol. 55, Issue 9
The ultraviolet absorption cross sections of CH3I temperature dependent gas and liquid phase measurements
journal, August 1995
- Fahr, Askar; Nayak, Akshaya K.; Kurylo, Michael J.
- Chemical Physics, Vol. 197, Issue 2
Subshell photoionization of Xe between 40 and 1000 eV
journal, April 1989
- Becker, U.; Szostak, D.; Kerkhoff, H. G.
- Physical Review A, Vol. 39, Issue 8
Medium and high resolution vacuum UV photoabsorption spectroscopy of methyl iodide (CH3I) and its deuterated isotopomers CD3I and CH2DI. A Rydberg series analysis
journal, November 2009
- Locht, R.; Leyh, B.; Jochims, H. W.
- Chemical Physics, Vol. 365, Issue 3
The High Resolution L 2,3 MM and M 4,5 NN Auger Spectra from Krypton and M 4,5 NN and N 4,5 OO Auger Spectra from Xenon
journal, August 1972
- Werme, L. O.; Bergmark, T.; Siegbahn, K.
- Physica Scripta, Vol. 6, Issue 2-3
New type of auger effect and its influence on the x-ray spectrum
journal, January 1935
- Coster, D.; L. Kronig, R. De
- Physica, Vol. 2, Issue 1-12
Absolute photoionization cross sections with ultra-high energy resolution for Ar, Kr, Xe and N2 in inner-shell ionization regions
journal, August 2007
- Kato, M.; Morishita, Y.; Oura, M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 160, Issue 1-3
Self-consistent-field calculations of core excited states
journal, March 2009
- Besley, Nicholas A.; Gilbert, Andrew T. B.; Gill, Peter M. W.
- The Journal of Chemical Physics, Vol. 130, Issue 12
Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses
journal, March 2016
- Boll, Rebecca; Erk, Benjamin; Coffee, Ryan
- Structural Dynamics, Vol. 3, Issue 4
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
Time-dependent density functional theory calculations of the spectroscopy of core electrons
journal, January 2010
- Besley, Nicholas A.; Asmuruf, Frans A.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 38
Recent progress in ESCA studies of gases
journal, January 1974
- Gelius, U.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 5, Issue 1
Imaging charge transfer in iodomethane upon x-ray photoabsorption
journal, July 2014
- Erk, B.; Boll, R.; Trippel, S.
- Science, Vol. 345, Issue 6194
Electron shake-up and correlation satellites and continuum shake-off distributions in X-Ray photoelectron spectra of the rare gas atoms
journal, January 1988
- Svensson, Svante; Eriksson, Bengt; Mårtensson, Nils
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 47
Inner shell excitation of CH 3F, CH 3Cl, CH 3Br and CH 3I by 2.5 keV electron impact
journal, January 1978
- Hitchcock, A. P.; Brion, C. E.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 13, Issue 3
Molecular photoionization cross sections by the local density LCAO Stieltjes imaging approach
journal, September 1995
- Stener, M.; Decleva, P.; Lisini, A.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 74, Issue 1
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004
- Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
- Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
Angle-resolved electron spectroscopy of the resonant Auger decay in xenon with meV energy resolution
journal, July 2011
- Söderström, Johan; Lindblad, Andreas; Grum-Grzhimailo, Alexei N.
- New Journal of Physics, Vol. 13, Issue 7
On the existence of a collective level in the Xe-atom
journal, March 1978
- Amusia, M. Ya.; Ivanov, V. K.
- Physics Letters A, Vol. 65, Issue 3
Augmented Gaussian basis sets for the elements K, Sc–Kr, Rb, and Y–Xe: Application in HF, MP2, and DFT calculations of molecular electric properties
journal, June 2013
- Martins, L. S. C.; de Souza, F. A. L.; Ceolin, G. A.
- Computational and Theoretical Chemistry, Vol. 1013
Lifetime Broadening and CI-Resonances Observed in ESCA
journal, October 1976
- Svensson, S.; Mårtensson, N.; Basilier, E.
- Physica Scripta, Vol. 14, Issue 4
3d photoionization of Xe, Cs and Ba and the collapse of the 4f wavefunction
journal, January 1999
- Arp, U.; Iemura, K.; Kutluk, G.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 32, Issue 5
Inner-shell photoemission from the iodine atom in I
journal, July 1984
- Lindle, D. W.; Kobrin, P. H.; Truesdale, C. M.
- Physical Review A, Vol. 30, Issue 1
Strong Dynamical Effects of Many-Electron Interactions in Photoelectron Spectra from 4 s and 4 p Core Levels
journal, October 1976
- Wendin, G.; Ohno, M.
- Physica Scripta, Vol. 14, Issue 4
A study of the photoionisation dynamics of chloromethane and iodomethane
journal, August 2006
- Holland, D. M. P.; Powis, I.; Öhrwall, G.
- Chemical Physics, Vol. 326, Issue 2-3
Time-Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules
book, March 2008
- Stolow, Albert; Underwood, Jonathan G.
- Advances in Chemical Physics
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
A theoretical CMS-X α treatment of CH3I photoionization dynamics: outer valence shell and iodine 4d levels
journal, December 1995
- Powis, Ivan
- Chemical Physics, Vol. 201, Issue 1
Electron‐molecule scattering and molecular photoionization using the multiple‐scattering method
journal, July 1974
- Dill, Dan; Dehmer, J. L.
- The Journal of Chemical Physics, Vol. 61, Issue 2
Photoionization of the Noble Gases: Cross Sections and Angular Distributions
journal, January 1972
- Kennedy, David J.; Manson, Steven Trent
- Physical Review A, Vol. 5, Issue 1
Electron Rearrangement Dynamics in Dissociating Molecules Accessed by Extreme Ultraviolet Pump-Probe Experiments
journal, August 2014
- Schnorr, K.; Senftleben, A.; Kurka, M.
- Physical Review Letters, Vol. 113, Issue 7
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
The absorption spectrum of CH 3 I in the extreme VUV
journal, May 1982
- O'Sullivan, G.
- Journal of Physics B: Atomic and Molecular Physics, Vol. 15, Issue 9
Vibrational and Vibronic Structure in the Valence Electron Spectra of CH 3 X Molecules (X=F, Cl, Br, I, OH)
journal, November 1977
- Karlsson, Leif; Jadrny, Reinhard; Mattsson, Lars
- Physica Scripta, Vol. 16, Issue 5-6
Extended photoionization calculations for xenon
journal, November 1989
- Kutzner, M.; Radojević, V.; Kelly, H. P.
- Physical Review A, Vol. 40, Issue 9
Analysis of post-collision interactions in Auger processes following near-threshold inner-shell photoionization
journal, July 1977
- Niehaus, A.
- Journal of Physics B: Atomic and Molecular Physics, Vol. 10, Issue 10
The plane grating and elliptical mirror: A new optical configuration for monochromators
journal, February 1982
- Petersen, Helmuth
- Optics Communications, Vol. 40, Issue 6
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
Collapse of the f-symmetric final-state wavefunction in the 3d excitation spectra of atomic Xe, Cs and Ba
journal, January 1984
- Sonntag, B.; Nagata, T.; Sato, Y.
- Journal of Physics B: Atomic and Molecular Physics, Vol. 17, Issue 2
Yields of multicharged Xe ions in the M-shell transition region
journal, April 1992
- Saito, N.; Suzuki, I. H.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 25, Issue 8
Subshell photoionization of Xe between 40 and 1000 eV
text, January 1989
- Becker, U.; Szostak, D.; Kerkhoff, H. G.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
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
Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
text, January 2018
- Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Works referencing / citing this record:
Absorption spectra at the iodine 3d ionisation threshold following the CH x I + ( x = 0–3) cation sequence
journal, January 2019
- Schubert, Kaja; Guda, Alexander A.; Mertens, Karolin
- Physical Chemistry Chemical Physics, Vol. 21, Issue 45
An experimental and theoretical study of the C 1s ionization satellites in CH 3 I
journal, June 2019
- Trofimov, A. B.; Belogolova, A. M.; Serebrennikova, S. A.
- The Journal of Chemical Physics, Vol. 150, Issue 22
Absorption spectra at the iodine 3d ionisation threshold following the CH$_x$I$^+$ ($x = 0-3$) cation sequence
text, January 2019
- Schubert, Kaja; Guda, Alexander A.; Mertens, Karolin
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Figures / Tables found in this record: