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Title: Photoionization of the I 4d and valence orbitals of methyl iodide

Abstract

Here, the photoabsorption and photoionization dynamics of the I 4d and valence orbitals in methyl iodide have been studied both experimentally and theoretically. Synchrotron radiation has been employed to measure the total ion yield in the vicinity of the I 4d ionization thresholds. The observed structure, due to excitations into Rydberg or valence states, has been assigned using transition energies and relative intensities computed with time-dependent density functional theory within the Tamm–Dancoff approximation. Photoelectron spectra, recorded with plane polarized radiation in two polarization geometries, have allowed the effect of autoionization on the valence electron angular distributions to be investigated. The spectra obtained at photon energies of 50.62 and 52.34 eV, coinciding respectively with the I 4d5/2 → σ* and 4d3/2 → σ* transitions, reveal, in addition to valence shell photoelectron bands, features not associated with simple photoionization of the parent molecule. High resolution photoelectron spectra of the I 4d main-lines display structure resulting from spin–orbit coupling and molecular field splitting. The binding energies of the five states contributing to the (I 4d)-1 ionization have been determined. The iodine (in CH3I) N45VV Auger spectrum has been measured and the observed structure has been assigned using the core hole binding energies derivedmore » in the present work together with established ionization energies of the doubly charged ion. The experimentally determined Auger electron angular distributions have been discussed in relation to the theoretical angular distribution parameter characterizing the spatial alignment of molecular axes in the (I 4d)-1 state.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [5];  [6];  [6]; ORCiD logo [6]; ORCiD logo [7]
  1. Univ. of College London (United Kingdom); Univ. of Ottawa, ON (Canada); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. European XFEL, Schenefeld (Germany)
  3. Kansas State Univ., Manhattan, KS (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Univ. of Nottingham (United Kingdom)
  6. Synchrotron SOLEIL, Gif-sur-Yvette (France)
  7. Daresbury Lab., Cheshire (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 & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC); Science and Technology Facilities Council (STFC)
OSTI Identifier:
1646792
Alternate Identifier(s):
OSTI ID: 1660713
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357; FG02-86ER13491; EP/N002148/1
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physics. B, Atomic, Molecular and Optical Physics
Additional Journal Information:
Journal Volume: 53; Journal Issue: 15; Journal ID: ISSN 0953-4075
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; photoionization; spin-orbit coupling; Auger electron; Rydberg and valence states

Citation Formats

Forbes, Ruaridh, De Fanis, Alberto, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D, and Holland, David M. P. Photoionization of the I 4d and valence orbitals of methyl iodide. United States: N. p., 2020. Web. https://doi.org/10.1088/1361-6455/ab8c5a.
Forbes, Ruaridh, De Fanis, Alberto, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D, & Holland, David M. P. Photoionization of the I 4d and valence orbitals of methyl iodide. United States. https://doi.org/10.1088/1361-6455/ab8c5a
Forbes, Ruaridh, De Fanis, Alberto, Rolles, Daniel, Pratt, Stephen T., Powis, Ivan, Besley, Nicholas A., Milosavljević, Aleksandar R., Nicolas, Christophe, Bozek, John D, and Holland, David M. P. Thu . "Photoionization of the I 4d and valence orbitals of methyl iodide". United States. https://doi.org/10.1088/1361-6455/ab8c5a. https://www.osti.gov/servlets/purl/1646792.
@article{osti_1646792,
title = {Photoionization of the I 4d and valence orbitals of methyl iodide},
author = {Forbes, Ruaridh and De Fanis, Alberto and Rolles, Daniel and Pratt, Stephen T. and Powis, Ivan and Besley, Nicholas A. and Milosavljević, Aleksandar R. and Nicolas, Christophe and Bozek, John D and Holland, David M. P.},
abstractNote = {Here, the photoabsorption and photoionization dynamics of the I 4d and valence orbitals in methyl iodide have been studied both experimentally and theoretically. Synchrotron radiation has been employed to measure the total ion yield in the vicinity of the I 4d ionization thresholds. The observed structure, due to excitations into Rydberg or valence states, has been assigned using transition energies and relative intensities computed with time-dependent density functional theory within the Tamm–Dancoff approximation. Photoelectron spectra, recorded with plane polarized radiation in two polarization geometries, have allowed the effect of autoionization on the valence electron angular distributions to be investigated. The spectra obtained at photon energies of 50.62 and 52.34 eV, coinciding respectively with the I 4d5/2 → σ* and 4d3/2 → σ* transitions, reveal, in addition to valence shell photoelectron bands, features not associated with simple photoionization of the parent molecule. High resolution photoelectron spectra of the I 4d main-lines display structure resulting from spin–orbit coupling and molecular field splitting. The binding energies of the five states contributing to the (I 4d)-1 ionization have been determined. The iodine (in CH3I) N45VV Auger spectrum has been measured and the observed structure has been assigned using the core hole binding energies derived in the present work together with established ionization energies of the doubly charged ion. The experimentally determined Auger electron angular distributions have been discussed in relation to the theoretical angular distribution parameter characterizing the spatial alignment of molecular axes in the (I 4d)-1 state.},
doi = {10.1088/1361-6455/ab8c5a},
journal = {Journal of Physics. B, Atomic, Molecular and Optical Physics},
number = 15,
volume = 53,
place = {United States},
year = {2020},
month = {6}
}

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Works referenced in this record:

Angular Distribution of Auger Electrons Following Photoionization
journal, July 1972


Spin-orbit interaction and molecular-field effects in the L 2 , 3 VV Auger-electron spectra of HCl
journal, September 1998

  • Fink, Reinhold F.; Kivilompolo, Mika; Aksela, Helena
  • Physical Review A, Vol. 58, Issue 3
  • DOI: 10.1103/physreva.58.1988

Electronic-state interference in the C 1 s excitation and decay of methyl chloride studied by angularly resolved Auger spectroscopy
journal, November 2017


On the angular distribution of Auger electrons following impact ionization
journal, April 1974


Angular distribution of molecular Auger electrons
journal, May 1996

  • Bonhoff, K.; Nahrup, S.; Lohmann, B.
  • The Journal of Chemical Physics, Vol. 104, Issue 20
  • DOI: 10.1063/1.471508

The relative importance of vibrational and ligand field splittings on core d-level photoelectron and NVV Auger spectra: high resolution core level photoelectron spectrum of the I 4d level of HI
journal, December 1991

  • Cutler, J. N.; Bancroft, G. M.; Tan, K. H.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 24, Issue 23
  • DOI: 10.1088/0953-4075/24/23/024

Atomic Autoionization Following Very Fast Dissociation of Core-Excited HBr
journal, May 1986


Angular distribution of ejected electrons in resonant Auger processes of Ar, Kr, and Xe
journal, February 1989

  • Carlson, Thomas A.; Mullins, David R.; Beall, Charles E.
  • Physical Review A, Vol. 39, Issue 3
  • DOI: 10.1103/physreva.39.1170

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
  • DOI: 10.1063/1.3092928

Theory and ab initio calculations of 2p photoabsorption spectra: The lowest Rydberg resonances in HCl
journal, December 1999

  • Fink, Reinhold F.; Kivilompolo, Mika; Aksela, Helena
  • The Journal of Chemical Physics, Vol. 111, Issue 22
  • DOI: 10.1063/1.480339

Theoretical study of inner-shell alignment of atoms in electron impact ionisation: angular distribution and polarisation of X-rays and Auger electrons
journal, August 1977

  • Berezhko, E. G.; Kabachnik, N. M.
  • Journal of Physics B: Atomic and Molecular Physics, Vol. 10, Issue 12
  • DOI: 10.1088/0022-3700/10/12/025

Auger decay of the C 1s−12π* resonance in carbon monoxide: Vibrationally and angularly resolved spectra
journal, December 1999

  • Kukk, E.; Bozek, J. D.; Cheng, W. -T.
  • The Journal of Chemical Physics, Vol. 111, Issue 21
  • DOI: 10.1063/1.480337

Potential-barrier effects in inner-shell photoionisation and their influence on the anisotropy of X-rays and Auger electrons
journal, May 1978

  • Berezhko, E. G.; Kabachnik, N. M.; Rostovsky, V. S.
  • Journal of Physics B: Atomic and Molecular Physics, Vol. 11, Issue 10
  • DOI: 10.1088/0022-3700/11/10/012

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


Angular Distribution of Molecular K -Shell Auger Electrons: Spectroscopy of Photoabsorption Anisotropy
journal, October 1980


Photoionization of chalcogen and halogen atoms: Cross sections and angular distributions
journal, September 1979

  • Manson, Steven T.; Msezane, Alfred; Starace, Anthony F.
  • Physical Review A, Vol. 20, Issue 3
  • DOI: 10.1103/physreva.20.1005

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


Excitation of the inner 4d shell of neutral iodine
journal, March 1981


Elucidating the origins of multimode vibrational coherences of polyatomic molecules induced by intense laser fields
journal, September 2017


Electron-spectroscopy study of inner-shell photoexcitation and ionization of Xe
journal, July 1983


On the Angular Distribution in Nuclear Reactions and Coincidence Measurements
journal, October 1948


Angular distribution of different vibrational components of the X and B states reached after resonant Auger decay of core-excited H2O: Experiment and theory
journal, February 2005

  • Hjelte, I.; Karlsson, L.; Svensson, S.
  • The Journal of Chemical Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.1850898

Ligand‐field splittings and core‐level linewidths in I 4 d photoelectron spectra of iodine molecules
journal, December 1992

  • Cutler, J. N.; Bancroft, G. M.; Tan, K. H.
  • The Journal of Chemical Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.463468

Auger electron spectroscopy of molecules: Theory for spin polarization following photoabsorption
journal, July 1992

  • Chandra, N.; Chakraborty, M.
  • The Journal of Chemical Physics, Vol. 97, Issue 1
  • DOI: 10.1063/1.463621

An unusual π* shape resonance in the near-threshold photoionization of S1 para -difluorobenzene
journal, June 2005

  • Bellm, Susan M.; Davies, Julia A.; Whiteside, Paul T.
  • The Journal of Chemical Physics, Vol. 122, Issue 22
  • DOI: 10.1063/1.1927523

Angular distribution of electronic decay following molecular and Rydberg excitations at the Cl 2 p edge of HCl
journal, April 1998


Connection between the angular distribution of Auger electrons and spectator autoionization electrons following 4d ionization/excitation in xenon
journal, December 1990

  • Kammerling, B.; Krassig, B.; Schmidt, V.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 23, Issue 24
  • DOI: 10.1088/0953-4075/23/24/009

Valence double ionization electron spectra of CH 3 F, CH 3 Cl and CH 3 I
journal, July 2017


Selectivity of the Br 3 d 1 Auger decays in HBr
journal, October 2018


Detailed analysis of the 3 d 1 4 p π 2 normal Auger spectra in HBr and DBr
journal, June 1999


Photoionization of closed-shell atoms: Hartree–Fock calculations of orientation and alignment
journal, October 2003


Angular distribution of Auger electrons from fixed-in-space and rotating C 1s→2π photoexcited CO: Theory
journal, January 2009

  • Fink, R. F.; Piancastelli, M. N.; Grum-Grzhimailo, A. N.
  • The Journal of Chemical Physics, Vol. 130, Issue 1
  • DOI: 10.1063/1.3042153

The absorption spectrum of CH 3 I in the extreme VUV
journal, May 1982


Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
journal, April 2018


Photoabsorption, photoionization, and Auger processes at the carbon K edge in C H 3 I
journal, February 2020


Double photoionisation spectra of HI, CH3I and CF3I from TOF-PEPECO measurements
journal, March 2005

  • Pilcher-Clayton, Anna; Eland, John H. D.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 142, Issue 3
  • DOI: 10.1016/j.elspec.2004.09.017

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

Spin-polarised Auger-electron spectroscopy of the d atomic shell. Model calculation for noble-gas atoms
journal, January 1988

  • Kabachnik, N. M.; Sazhina, I. P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 21, Issue 2
  • DOI: 10.1088/0953-4075/21/2/011

Trends in 4 d -subshell photoabsorption along the iodine isonuclear sequence: I, I + , and I 2 +
journal, May 1996


Isotope effects in the auger electron spectra of HBr and DBr
journal, May 1989


Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103
journal, January 1985


Inner-shell and outer-shell excitation of HCl, HBr and Br 2 by electron impact with high resolution
journal, March 1984

  • Shaw, D. A.; Cvejanovic, D.; King, G. C.
  • Journal of Physics B: Atomic and Molecular Physics, Vol. 17, Issue 6
  • DOI: 10.1088/0022-3700/17/6/026

The NVV Auger electron spectrum of the HI molecule
journal, October 1989

  • Karlsson, L.; Svensson, S.; Baltzer, P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 22, Issue 19
  • DOI: 10.1088/0953-4075/22/19/014

Observation of nonisotropic Auger angular distribution in the C(1 s ) shape resonance of CO
journal, August 1993


The importance of ligand-field splitting in the interpretation of the HBr Br3d pre-edge photoabsorption (EELS) spectrum, the Br3d photoelectron spectrum, and the MVV Auger spectrum
journal, April 1994

  • Liu, Z. F.; Bancroft, G. M.; Tan, K. H.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 67, Issue 2
  • DOI: 10.1016/0368-2048(94)80007-3

Relaxation of the 4 d →5 p resonance in atomic iodine
journal, May 1990


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


VUV spectroscopy of CH3Cl and CH3I
journal, January 2007


On the angular distribution of Auger electrons
journal, October 1971


Auger electron spectroscopy of molecules: Theory for angular and spin correlations with photoelectrons
journal, November 1993

  • Chandra, N.; Chakraborty, M.
  • The Journal of Chemical Physics, Vol. 99, Issue 10
  • DOI: 10.1063/1.465713

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

An investigation of dissociative resonant photoionization in HCl and DCl using two-dimensional photoelectron spectroscopy
journal, May 2005

  • Sokell, E.; Wills, A. A.; Wiedenhoeft, M.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 38, Issue 10
  • DOI: 10.1088/0953-4075/38/10/011

Energy partitioning following photodissociation of methyl iodide in the A band: A velocity mapping study
journal, January 1999

  • Eppink, A. T. J. B.; Parker, D. H.
  • The Journal of Chemical Physics, Vol. 110, Issue 2
  • DOI: 10.1063/1.478051

Angular distribution in xenon M 4 , 5 N 4 , 5 N 4 , 5 Auger decay
journal, January 1999


Refinement in the analysis of molecular Auger electron spectra: The 2 p 1 3 p π 2 spectra of HCl and DCl
journal, March 2002


Dynamics of the C 1 s π * excitation and decay in CO 2 probed by vibrationally and angularly resolved Auger spectroscopy
journal, October 2015


Femtosecond Dissociation of Core-Excited HCl Monitored by Frequency Detuning
journal, October 1997


Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation
journal, July 2016

  • Drescher, L.; Galbraith, M. C. E.; Reitsma, G.
  • The Journal of Chemical Physics, Vol. 145, Issue 1
  • DOI: 10.1063/1.4955212

Time-dependent density functional theory within the Tamm–Dancoff approximation
journal, December 1999


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
  • DOI: 10.1016/j.cplett.2004.06.011

Auger decay of the dissociating core‐excited states in the HCl and DCl molecules
journal, March 1996

  • Kukk, E.; Aksela, H.; Sairanen, O. ‐P.
  • The Journal of Chemical Physics, Vol. 104, Issue 12
  • DOI: 10.1063/1.471542

Rovibrational photoionization dynamics of methyl and its isotopomers studied by high-resolution photoionization and photoelectron spectroscopy
journal, September 2006

  • Schulenburg, A. M.; Alcaraz, Ch.; Grassi, G.
  • The Journal of Chemical Physics, Vol. 125, Issue 10
  • DOI: 10.1063/1.2348875

Angular distribution in resonant Auger spectra of xenon excited below the 3 d 5 / 2 ionization threshold
journal, February 2001


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

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


Analysis of the angular distribution of Auger electrons in a Xe atom
journal, October 2003

  • Elizarov, A. Yu.; Tupitsyn, I. I.
  • Journal of Experimental and Theoretical Physics, Vol. 97, Issue 4
  • DOI: 10.1134/1.1625056

Inner-shell photoemission from the iodine atom in CH 3 I
journal, July 1984


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


Imaging the Temporal Evolution of Molecular Orbitals during Ultrafast Dissociation
journal, December 2016


Ligand-Field Splittings on Core Levels of Main Group Compounds and Metal Surfaces from Photoelectron Spectra
journal, February 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

Experimental and theoretical study of the Auger cascade following 4d $\rightarrow$ 6p photoexcitation in Xe
journal, July 2002

  • Kitajima, M.; Okamoto, M.; Hoshino, M.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 35, Issue 15
  • DOI: 10.1088/0953-4075/35/15/307

Valence and inner shell electronic processes in dissociative double photoionization of CH3I
journal, June 1986


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

Comment on the NVV Auger electron spectrum of the HI molecule
journal, December 1991

  • Karlsson, L.; Svensson, S.; Baltzer, P.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 24, Issue 23
  • DOI: 10.1088/0953-4075/24/23/006

Effect of intermediate coupling on angular distribution of Auger electrons
journal, February 1992


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


Photoionization Decay of Core Excited Molecules
journal, January 1987


Photonization-produced alignment of Cd
journal, April 1982


The effect of many-electron correlations on the angular distribution and spin polarisation of Auger electrons in Kr and Xe
journal, November 1988

  • Kabachnik, N. M.; Sazhina, I. P.; Lee, I. S.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 21, Issue 22
  • DOI: 10.1088/0953-4075/21/22/008

M 4 , 5 N 4 , 5 X Auger electron spectra of iodine and xenon. Many-body effects
journal, February 1979


The gas phase L2,3VV Auger electron spectra of chlorine in XCl (X=H, D, Li, Na, K) molecules
journal, July 2000

  • Kivilompolo, Mika; Kivimäki, Antti; Aksela, Helena
  • The Journal of Chemical Physics, Vol. 113, Issue 2
  • DOI: 10.1063/1.481914

Alignment after Xe L 3 photoionization by synchrotron radiation
journal, May 2003

  • K. st, H.; Kleiman, U.; Mehlhorn, W.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 36, Issue 10
  • DOI: 10.1088/0953-4075/36/10/315

Direct Observation of the Transition-State Region in the Photodissociation of CH 3 I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy
journal, December 2015

  • Attar, Andrew R.; Bhattacherjee, Aditi; Leone, Stephen R.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
  • DOI: 10.1021/acs.jpclett.5b02489