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

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.

doi:10.1063/1.5035496

Title: Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide

Journal Article · Sun Oct 14 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5035496· OSTI ID:1487114

Forbes, Ruaridh ^[1]; De Fanis, Alberto ^[2]; Bomme, Cédric ^[3];

^[4]; Pratt, Stephen T. ^[5];

^[6];

^[6]; Simon, Marc ^[7]; Nandi, Saikat ^[8];

^[8]; Nicolas, Christophe ^[8]; Bozek, John D. ^[8]; Underwood, Jonathan G. ^[9]; Holland, David M. P. ^[10]

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).

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 3d_5/2 and 3d_3/2 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 3d_5/2 → εf and the I 3d_3/2 → 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.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Science and Technology Facilities Council (STFC) (United Kingdom)

Grant/Contract Number:: AC02-06CH11357; FG02-86ER13491

OSTI ID:: 1487114

Alternate ID(s):: OSTI ID: 1476694

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 14; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 13 works

Citation information provided by
Web of Science

References (48)

Electron distribution in the xenon fluorides and xenon oxide tetrafluoride by ESCA and evidence for orbital independence in the xenon-fluorine bonding Carroll, T. X.; Shaw, R. W.; Thomas, T. D. Journal of the American Chemical Society, Vol. 96, Issue 7 https://doi.org/10.1021/ja00814a001	journal	April 1974
Newly Observed Structure in the Photoionization Continua of Kr and Xe below 160 Å Codling, K.; Madden, R. P. Applied Optics, Vol. 4, Issue 11 https://doi.org/10.1364/ao.4.001431	journal	January 1965
3d photoabsorption in gaseous and solid xenon Yagci, O.; Wilson, J. E. Journal of Physics C: Solid State Physics, Vol. 16, Issue 2 https://doi.org/10.1088/0022-3719/16/2/021	journal	January 1983
Inner-shell photoionization and core-hole decay of Xe and XeF2 Southworth, Stephen H.; Wehlitz, Ralf; Picón, Antonio The Journal of Chemical Physics, Vol. 142, Issue 22 https://doi.org/10.1063/1.4922208	journal	June 2015
Angular Distribution of Photoelectrons Cooper, J.; Zare, R. N. The Journal of Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1063/1.1668742	journal	January 1968
Photoionization of atoms using synchrotron radiation Schmidt, V. Reports on Progress in Physics, Vol. 55, Issue 9 https://doi.org/10.1088/0034-4885/55/9/003	journal	September 1992
The ultraviolet absorption cross sections of CH3I temperature dependent gas and liquid phase measurements Fahr, Askar; Nayak, Akshaya K.; Kurylo, Michael J. Chemical Physics, Vol. 197, Issue 2 https://doi.org/10.1016/0301-0104(95)00172-k	journal	August 1995
Subshell photoionization of Xe between 40 and 1000 eV Becker, U.; Szostak, D.; Kerkhoff, H. G. Physical Review A, Vol. 39, Issue 8 https://doi.org/10.1103/physreva.39.3902	journal	April 1989
Medium and high resolution vacuum UV photoabsorption spectroscopy of methyl iodide (CH3I) and its deuterated isotopomers CD3I and CH2DI. A Rydberg series analysis Locht, R.; Leyh, B.; Jochims, H. W. Chemical Physics, Vol. 365, Issue 3 https://doi.org/10.1016/j.chemphys.2009.09.025	journal	November 2009
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 Werme, L. O.; Bergmark, T.; Siegbahn, K. Physica Scripta, Vol. 6, Issue 2-3 https://doi.org/10.1088/0031-8949/6/2-3/008	journal	August 1972
New type of auger effect and its influence on the x-ray spectrum Coster, D.; L. Kronig, R. De Physica, Vol. 2, Issue 1-12 https://doi.org/10.1016/s0031-8914(35)90060-x	journal	January 1935
Absolute photoionization cross sections with ultra-high energy resolution for Ar, Kr, Xe and N2 in inner-shell ionization regions Kato, M.; Morishita, Y.; Oura, M. Journal of Electron Spectroscopy and Related Phenomena, Vol. 160, Issue 1-3 https://doi.org/10.1016/j.elspec.2007.06.003	journal	August 2007
Self-consistent-field calculations of core excited states Besley, Nicholas A.; Gilbert, Andrew T. B.; Gill, Peter M. W. The Journal of Chemical Physics, Vol. 130, Issue 12 https://doi.org/10.1063/1.3092928	journal	March 2009
Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses Boll, Rebecca; Erk, Benjamin; Coffee, Ryan Structural Dynamics, Vol. 3, Issue 4 https://doi.org/10.1063/1.4944344	journal	March 2016
Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cédric The Journal of Chemical Physics, Vol. 149, Issue 9 https://doi.org/10.1063/1.5045640	journal	September 2018
Time-dependent density functional theory calculations of the spectroscopy of core electrons Besley, Nicholas A.; Asmuruf, Frans A. Physical Chemistry Chemical Physics, Vol. 12, Issue 38 https://doi.org/10.1039/c002207a	journal	January 2010
Recent progress in ESCA studies of gases Gelius, U. Journal of Electron Spectroscopy and Related Phenomena, Vol. 5, Issue 1 https://doi.org/10.1016/0368-2048(74)85064-4	journal	January 1974
Imaging charge transfer in iodomethane upon x-ray photoabsorption Erk, B.; Boll, R.; Trippel, S. Science, Vol. 345, Issue 6194 https://doi.org/10.1126/science.1253607	journal	July 2014
Electron shake-up and correlation satellites and continuum shake-off distributions in X-Ray photoelectron spectra of the rare gas atoms Svensson, Svante; Eriksson, Bengt; Mårtensson, Nils Journal of Electron Spectroscopy and Related Phenomena, Vol. 47 https://doi.org/10.1016/0368-2048(88)85020-5	journal	January 1988
Inner shell excitation of CH 3F, CH 3Cl, CH 3Br and CH 3I by 2.5 keV electron impact Hitchcock, A. P.; Brion, C. E. Journal of Electron Spectroscopy and Related Phenomena, Vol. 13, Issue 3 https://doi.org/10.1016/0368-2048(78)85027-0	journal	January 1978
Molecular photoionization cross sections by the local density LCAO Stieltjes imaging approach Stener, M.; Decleva, P.; Lisini, A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 74, Issue 1 https://doi.org/10.1016/0368-2048(95)02357-7	journal	September 1995
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) Yanai, Takeshi; Tew, David P.; Handy, Nicholas C. Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57 https://doi.org/10.1016/j.cplett.2004.06.011	journal	July 2004
Angle-resolved electron spectroscopy of the resonant Auger decay in xenon with meV energy resolution Söderström, Johan; Lindblad, Andreas; Grum-Grzhimailo, Alexei N. New Journal of Physics, Vol. 13, Issue 7 https://doi.org/10.1088/1367-2630/13/7/073014	journal	July 2011
On the existence of a collective level in the Xe-atom Amusia, M. Ya.; Ivanov, V. K. Physics Letters A, Vol. 65, Issue 3 https://doi.org/10.1016/0375-9601(78)90153-6	journal	March 1978
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 Martins, L. S. C.; de Souza, F. A. L.; Ceolin, G. A. Computational and Theoretical Chemistry, Vol. 1013 https://doi.org/10.1016/j.comptc.2013.03.004	journal	June 2013
Lifetime Broadening and CI-Resonances Observed in ESCA Svensson, S.; Mårtensson, N.; Basilier, E. Physica Scripta, Vol. 14, Issue 4 https://doi.org/10.1088/0031-8949/14/4/004	journal	October 1976
3d photoionization of Xe, Cs and Ba and the collapse of the 4f wavefunction Arp, U.; Iemura, K.; Kutluk, G. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 32, Issue 5 https://doi.org/10.1088/0953-4075/32/5/019	journal	January 1999
Inner-shell photoemission from the iodine atom in ${CH}_{3}$ I Lindle, D. W.; Kobrin, P. H.; Truesdale, C. M. Physical Review A, Vol. 30, Issue 1 https://doi.org/10.1103/physreva.30.239	journal	July 1984
Strong Dynamical Effects of Many-Electron Interactions in Photoelectron Spectra from 4 s and 4 p Core Levels Wendin, G.; Ohno, M. Physica Scripta, Vol. 14, Issue 4 https://doi.org/10.1088/0031-8949/14/4/005	journal	October 1976
A study of the photoionisation dynamics of chloromethane and iodomethane Holland, D. M. P.; Powis, I.; Öhrwall, G. Chemical Physics, Vol. 326, Issue 2-3 https://doi.org/10.1016/j.chemphys.2006.03.017	journal	August 2006
Time-Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules Stolow, Albert; Underwood, Jonathan G. Advances in Chemical Physics https://doi.org/10.1002/9780470259498.ch6	book	March 2008
Resolution and signal‐to‐background enhancement in gas‐phase electron spectroscopy Baltzer, P.; Karlsson, L.; Lundqvist, M. Review of Scientific Instruments, Vol. 64, Issue 8 https://doi.org/10.1063/1.1143957	journal	August 1993
A theoretical CMS-X α treatment of CH3I photoionization dynamics: outer valence shell and iodine 4d levels Powis, Ivan Chemical Physics, Vol. 201, Issue 1 https://doi.org/10.1016/0301-0104(95)00299-0	journal	December 1995
Electron‐molecule scattering and molecular photoionization using the multiple‐scattering method Dill, Dan; Dehmer, J. L. The Journal of Chemical Physics, Vol. 61, Issue 2 https://doi.org/10.1063/1.1681947	journal	July 1974
Photoionization of the Noble Gases: Cross Sections and Angular Distributions Kennedy, David J.; Manson, Steven Trent Physical Review A, Vol. 5, Issue 1 https://doi.org/10.1103/physreva.5.227	journal	January 1972
Electron Rearrangement Dynamics in Dissociating $I_{2}^{n +}$ Molecules Accessed by Extreme Ultraviolet Pump-Probe Experiments Schnorr, K.; Senftleben, A.; Kurka, M. Physical Review Letters, Vol. 113, Issue 7 https://doi.org/10.1103/physrevlett.113.073001	journal	August 2014
A method to determine a transmission correction for electron spectrometers using synchrotron radiation Jauhiainen, J.; Ausmees, A.; Kivimäkia, A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 69, Issue 3 https://doi.org/10.1016/0368-2048(94)02197-8	journal	October 1994
The absorption spectrum of CH ₃ I in the extreme VUV O'Sullivan, G. Journal of Physics B: Atomic and Molecular Physics, Vol. 15, Issue 9 https://doi.org/10.1088/0022-3700/15/9/005	journal	May 1982
Vibrational and Vibronic Structure in the Valence Electron Spectra of CH ₃ X Molecules (X=F, Cl, Br, I, OH) Karlsson, Leif; Jadrny, Reinhard; Mattsson, Lars Physica Scripta, Vol. 16, Issue 5-6 https://doi.org/10.1088/0031-8949/16/5-6/010	journal	November 1977
Extended photoionization calculations for xenon Kutzner, M.; Radojević, V.; Kelly, H. P. Physical Review A, Vol. 40, Issue 9 https://doi.org/10.1103/physreva.40.5052	journal	November 1989
Analysis of post-collision interactions in Auger processes following near-threshold inner-shell photoionization Niehaus, A. Journal of Physics B: Atomic and Molecular Physics, Vol. 10, Issue 10 https://doi.org/10.1088/0022-3700/10/10/014	journal	July 1977
The plane grating and elliptical mirror: A new optical configuration for monochromators Petersen, Helmuth Optics Communications, Vol. 40, Issue 6 https://doi.org/10.1016/0030-4018(82)90040-2	journal	February 1982
The influence of the bromine atom Cooper minimum on the photoelectron angular distributions and branching ratios of the four outermost bands of bromobenzene Powis, I.; Holland, D. M. P.; Antonsson, E. The Journal of Chemical Physics, Vol. 143, Issue 14 https://doi.org/10.1063/1.4931642	journal	October 2015
Collapse of the f-symmetric final-state wavefunction in the 3d excitation spectra of atomic Xe, Cs and Ba Sonntag, B.; Nagata, T.; Sato, Y. Journal of Physics B: Atomic and Molecular Physics, Vol. 17, Issue 2 https://doi.org/10.1088/0022-3700/17/2/003	journal	January 1984
Yields of multicharged Xe ions in the M-shell transition region Saito, N.; Suzuki, I. H. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 25, Issue 8 https://doi.org/10.1088/0953-4075/25/8/013	journal	April 1992
Subshell photoionization of Xe between 40 and 1000 eV Becker, U.; Szostak, D.; Kerkhoff, H. G. Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2017-04033	text	January 1989
Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide Forbes, Ruaridh; De Fanis, Alberto; Bomme, Cedric Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2019-00089	text	January 2018
Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2018-01956	text	January 2018

Cited By (3)

Absorption spectra at the iodine 3d ionisation threshold following the CH x I + ( x = 0–3) cation sequence Schubert, Kaja; Guda, Alexander A.; Mertens, Karolin Physical Chemistry Chemical Physics, Vol. 21, Issue 45 https://doi.org/10.1039/c9cp04640b	journal	January 2019
An experimental and theoretical study of the C 1s ionization satellites in CH ₃ I Trofimov, A. B.; Belogolova, A. M.; Serebrennikova, S. A. The Journal of Chemical Physics, Vol. 150, Issue 22 https://doi.org/10.1063/1.5099699	journal	June 2019
Absorption spectra at the iodine 3d ionisation threshold following the CH$_x$I$^+$ ($x = 0-3$) cation sequence Schubert, Kaja; Guda, Alexander A.; Mertens, Karolin Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2019-04330	text	January 2019