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Title: Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO) 5, Fe(CO) 4, and Fe(CO) 3

Abstract

The prototypical photoinduced dissociation of Fe(CO) 5 in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO) 5 successively dissociates to Fe(CO) 4 and Fe(CO) 3 along a pathway where both fragments retain the singlet multiplicity of Fe(CO) 5. The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO) 4 and Fe(CO) 3 with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valence-orbital interactions upon Fe–CO dissociation, thereby validating fundamental theoretical concepts in Fe–CO bonding. Chemical shifts of CO 3σ inner-valence and Fe 3p core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. Lastly, it could also serve as a benchmark for how charge and spin density changes in molecular dissociation and excited-state dynamicsmore » are expressed in valence and core-level photoelectron spectroscopy.« less

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [4];  [6];  [7];  [8];  [5];  [9]; ORCiD logo [2]; ORCiD logo [1]
  1. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  2. Stockholm Univ., Stockholm (Sweden)
  3. European XFEL GmbH, Schenefeld (Germany)
  4. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  5. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany)
  6. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Stockholm Univ., Stockholm (Sweden)
  8. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  9. European XFEL GmbH, Schenefeld (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1468956
Grant/Contract Number:  
[AC02-76SF00515; EXC1074; 05K10PK2]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 149; Journal Issue: 4]; 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

Leitner, T., Josefsson, I., Mazza, T., Miedema, P. S., Schröder, H., Beye, M., Kunnus, K., Schreck, S., Düsterer, S., Föhlisch, A., Meyer, M., Odelius, M., and Wernet, Ph. Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3. United States: N. p., 2018. Web. doi:10.1063/1.5035149.
Leitner, T., Josefsson, I., Mazza, T., Miedema, P. S., Schröder, H., Beye, M., Kunnus, K., Schreck, S., Düsterer, S., Föhlisch, A., Meyer, M., Odelius, M., & Wernet, Ph. Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3. United States. doi:10.1063/1.5035149.
Leitner, T., Josefsson, I., Mazza, T., Miedema, P. S., Schröder, H., Beye, M., Kunnus, K., Schreck, S., Düsterer, S., Föhlisch, A., Meyer, M., Odelius, M., and Wernet, Ph. Fri . "Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3". United States. doi:10.1063/1.5035149. https://www.osti.gov/servlets/purl/1468956.
@article{osti_1468956,
title = {Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)5, Fe(CO)4, and Fe(CO)3},
author = {Leitner, T. and Josefsson, I. and Mazza, T. and Miedema, P. S. and Schröder, H. and Beye, M. and Kunnus, K. and Schreck, S. and Düsterer, S. and Föhlisch, A. and Meyer, M. and Odelius, M. and Wernet, Ph.},
abstractNote = {The prototypical photoinduced dissociation of Fe(CO)5 in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)5 successively dissociates to Fe(CO)4 and Fe(CO)3 along a pathway where both fragments retain the singlet multiplicity of Fe(CO)5. The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)4 and Fe(CO)3 with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valence-orbital interactions upon Fe–CO dissociation, thereby validating fundamental theoretical concepts in Fe–CO bonding. Chemical shifts of CO 3σ inner-valence and Fe 3p core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. Lastly, it could also serve as a benchmark for how charge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy.},
doi = {10.1063/1.5035149},
journal = {Journal of Chemical Physics},
number = [4],
volume = [149],
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

Time-resolved photoelectron spectroscopy of polyatomic molecules using 42-nm vacuum ultraviolet laser based on high harmonics generation
journal, September 2017


The soft x-ray free-electron laser FLASH at DESY: beamlines, diagnostics and end-stations
journal, February 2009


Binding Energies and Chemical Shifts in ESCA
journal, March 1974


An experiment for two-color photoionization using high intensity extreme-UV free electron and near-IR laser pulses
journal, December 2007

  • Radcliffe, P.; Düsterer, S.; Azima, A.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 583, Issue 2-3
  • DOI: 10.1016/j.nima.2007.09.014

Ultrafast Dynamics of a Nucleobase Analogue Illuminated by a Short Intense X-ray Free Electron Laser Pulse
journal, June 2016


Photochemistry of metal carbonyls
journal, August 1974


Time-Resolved Dynamics in N2O4 Probed Using High Harmonic Generation
journal, November 2008


Theoretical aspects of the photochemistry of organometallics. 3. Potential energy curves for the photodissociation of pentacarbonyliron (Fe(CO)5)
journal, October 1984

  • Daniel, Chantal; Benard, Marc; Dedieu, Alain
  • The Journal of Physical Chemistry, Vol. 88, Issue 21
  • DOI: 10.1021/j150665a004

Ultrafast Electron Diffraction of Transient [Fe(CO)4]: Determination of Molecular Structure and Reaction Pathway
journal, April 2001


Performance of the monochromator beamline at FLASH
journal, July 2007

  • Wellhöfer, M.; Martins, M.; Wurth, W.
  • Journal of Optics A: Pure and Applied Optics, Vol. 9, Issue 7
  • DOI: 10.1088/1464-4258/9/7/030

A Chemical View on X-ray Photoelectron Spectroscopy: the ESCA Molecule and Surface-to-Bulk XPS Shifts
journal, December 2017

  • Delesma, Francisco A.; Van den Bossche, Maxime; Grönbeck, Henrik
  • ChemPhysChem, Vol. 19, Issue 2
  • DOI: 10.1002/cphc.201701135

Single-shot characterization of independent femtosecond extreme ultraviolet free electron and infrared laser pulses
journal, March 2007

  • Radcliffe, P.; Düsterer, S.; Azima, A.
  • Applied Physics Letters, Vol. 90, Issue 13
  • DOI: 10.1063/1.2716360

Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source
journal, January 2017


The ultrafast photodissociation of Fe(CO)5 in the gas phase
journal, April 1998

  • Bañares, L.; Baumert, T.; Bergt, M.
  • The Journal of Chemical Physics, Vol. 108, Issue 14
  • DOI: 10.1063/1.475991

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
  • DOI: 10.1063/1.4944344

Resonant photoemission at the iron M-edge of Fe(CO) 5
journal, October 2013

  • Sistrunk, E.; Grilj, J.; McFarland, B. K.
  • The Journal of Chemical Physics, Vol. 139, Issue 16
  • DOI: 10.1063/1.4827093

The FLASH pump–probe laser system: Setup, characterization and optical beamlines
journal, April 2011

  • Redlin, H.; Al-Shemmary, A.; Azima, A.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 635, Issue 1
  • DOI: 10.1016/j.nima.2010.09.159

Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling
journal, August 2015

  • Grell, Gilbert; Bokarev, Sergey I.; Winter, Bernd
  • The Journal of Chemical Physics, Vol. 143, Issue 7
  • DOI: 10.1063/1.4928511

Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy
journal, December 2016

  • Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.
  • The Journal of Chemical Physics, Vol. 145, Issue 23
  • DOI: 10.1063/1.4972258

Quantum electrodynamical corrections to the fine structure of helium
journal, January 1974


Femtosecond M 2,3 -Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe 2 O 3
journal, October 2013

  • Vura-Weis, Josh; Jiang, Chang-Ming; Liu, Chong
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
  • DOI: 10.1021/jz401997d

The monochromator beamline at FLASH: performance, capabilities and upgrade plans
journal, September 2011


Core holes in chemisorbed atoms
journal, September 1977


Observation of coordinatively unsaturated intermediates following the pulsed UV photolysis of iron pentacarbonyl (Fe(CO)5)
journal, May 1983

  • Ouderkirk, A. J.; Wermer, Paul; Schultz, N. L.
  • Journal of the American Chemical Society, Vol. 105, Issue 10
  • DOI: 10.1021/ja00348a076

Femtosecond Multidimensional Imaging of a Molecular Dissociation
journal, January 2006


Imaging charge transfer in iodomethane upon x-ray photoabsorption
journal, July 2014


Explanation of the satellite structure observed in the photoemission spectra of coordinated CO
journal, May 1981


The Nature of the Bonding in Transition-Metal Compounds
journal, February 2000

  • Frenking, Gernot; Fröhlich, Nikolaus
  • Chemical Reviews, Vol. 100, Issue 2
  • DOI: 10.1021/cr980401l

A comparison of surface electron spectroscopies
journal, July 1985


Time-resolved studies with FELs
journal, October 2015


Time-resolved high-harmonic spectroscopy of valence electron dynamics
journal, March 2013


High resolution x‐ray photoelectron spectroscopy study of Cr(CO) 6 in the gas phase
journal, June 1992

  • Nilsson, A.; Mårtensson, N.; Svensson, S.
  • The Journal of Chemical Physics, Vol. 96, Issue 12
  • DOI: 10.1063/1.462284

Modelling spin-forbidden reactions: recombination of carbon monoxide with iron tetracarbonyl
journal, January 2003

  • Harvey, Jeremy N.; Aschi, Massimiliano
  • Faraday Discussions, Vol. 124
  • DOI: 10.1039/b211871h

Structure and reactions of matrix-isolated tetracarbonyliron(0)
journal, January 1974

  • Poliakoff, Martyn; Turner, James J.
  • Journal of the Chemical Society, Dalton Transactions, Issue 20
  • DOI: 10.1039/dt9740002276

Real-Time Observation of Surface Bond Breaking with an X-ray Laser
journal, March 2013


Photoelectron spectra of transition-metal carbonyl complexes: comparison with the spectra of adsorbed CO
journal, August 1978


Monochromator beamline for FLASH
journal, November 2006

  • Martins, M.; Wellhöfer, M.; Hoeft, J. T.
  • Review of Scientific Instruments, Vol. 77, Issue 11
  • DOI: 10.1063/1.2364148

Femtosecond Dynamics of Fe(CO) 5 Photodissociation at 267 nm Studied by Transient Ionization
journal, March 2000

  • Trushin, S. A.; Fuss, W.; Kompa, K. L.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 10
  • DOI: 10.1021/jp992474u

The Structure of [Fe(CO)4]—An Important New Chapter in a Long-Running Story
journal, August 2001


The Jahn–Teller effect in the photoelectron spectrum of iron pentacarbonyl
journal, September 1981

  • Hubbard, John L.; Lichtenberger, Dennis L.
  • The Journal of Chemical Physics, Vol. 75, Issue 6
  • DOI: 10.1063/1.442407

Picosecond X-ray absorption measurements of the ligand substitution dynamics of Fe(CO)5 in ethanol
journal, January 2011

  • Ahr, Brian; Chollet, Matthieu; Adams, Bernhard
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 13
  • DOI: 10.1039/c0cp01856b

New Relativistic ANO Basis Sets for Transition Metal Atoms
journal, July 2005

  • Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke
  • The Journal of Physical Chemistry A, Vol. 109, Issue 29
  • DOI: 10.1021/jp0581126

An ab initio study of Fe(CO) n , n =1,5, and Cr(CO) 6
journal, February 1991

  • Barnes, Leslie A.; Rosi, Marzio; Bauschlicher, Charles W.
  • The Journal of Chemical Physics, Vol. 94, Issue 3
  • DOI: 10.1063/1.459924

Gas detectors for x-ray lasers
journal, May 2008

  • Tiedtke, K.; Feldhaus, J.; Hahn, U.
  • Journal of Applied Physics, Vol. 103, Issue 9
  • DOI: 10.1063/1.2913328

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980


Operation of a free-electron laser from the extreme ultraviolet to the water window
journal, June 2007


Femtosecond Time-Resolved Photoelectron Spectroscopy
journal, April 2004

  • Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.
  • Chemical Reviews, Vol. 104, Issue 4
  • DOI: 10.1021/cr020683w

On the origin of core-level binding energy shifts
journal, December 1995


Femtosecond photodissociation dynamics of Fe(CO)5 in the gas phase
journal, March 1997


Ultrafast X-ray Auger probing of photoexcited molecular dynamics
journal, June 2014

  • McFarland, B. K.; Farrell, J. P.; Miyabe, S.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5235

Free-Electron Lasers: New Avenues in Molecular Physics and Photochemistry
journal, May 2012


Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy
journal, December 2015


Electron Dynamics in the Core-Excited CS 2 Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy
journal, August 2015


Transient photoelectron spectroscopy of the dissociative Br2(Πu1) state
journal, November 2007

  • Strasser, Daniel; Goulay, Fabien; Leone, Stephen R.
  • The Journal of Chemical Physics, Vol. 127, Issue 18
  • DOI: 10.1063/1.2803923

Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction
journal, April 2017

  • Attar, Andrew R.; Bhattacherjee, Aditi; Pemmaraju, C. D.
  • Science, Vol. 356, Issue 6333
  • DOI: 10.1126/science.aaj2198

On the photofragmentation of Fe(CO) 5 . II. Molecular orbital studies of Fe(CO) n , 1≥ n ≥5
journal, January 1984

  • Guenzburger, Diana; Baggio‐Saitovitch, Elisa; De Paoli, Marco A.
  • The Journal of Chemical Physics, Vol. 80, Issue 2
  • DOI: 10.1063/1.446780

X-ray emission spectroscopy and density functional study of CO/Fe(100)
journal, January 2012

  • Gladh, J.; Öberg, H.; Li, Jibiao
  • The Journal of Chemical Physics, Vol. 136, Issue 3
  • DOI: 10.1063/1.3675834

The restricted active space self-consistent-field method, implemented with a split graph unitary group approach
journal, July 1990

  • Malmqvist, Per Aake.; Rendell, Alistair.; Roos, Bjoern O.
  • The Journal of Physical Chemistry, Vol. 94, Issue 14
  • DOI: 10.1021/j100377a011

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015

  • Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
  • Journal of Computational Chemistry, Vol. 37, Issue 5
  • DOI: 10.1002/jcc.24221

Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)5 via a singlet pathway upon excitation at 266 nm
journal, June 2017

  • Wernet, Ph.; Leitner, T.; Josefsson, I.
  • The Journal of Chemical Physics, Vol. 146, Issue 21
  • DOI: 10.1063/1.4984774

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution
journal, April 2015


Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH
journal, February 2016

  • Kunnus, K.; Josefsson, I.; Rajkovic, I.
  • Structural Dynamics, Vol. 3, Issue 4
  • DOI: 10.1063/1.4941602

Time-Resolved Photoelectron Spectroscopy of Dissociating 1,2-Butadiene Molecules by High Harmonic Pulses
journal, June 2015

  • Iikubo, Ryo; Fujiwara, Takehisa; Sekikawa, Taro
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 13
  • DOI: 10.1021/acs.jpclett.5b00943

Shedding light on organometallic reactions: the characterization of tetracarbonyliron (Fe(CO)4), a prototypical reaction intermediate
journal, November 1987

  • Poliakoff, Martyn; Weitz, Eric
  • Accounts of Chemical Research, Vol. 20, Issue 11
  • DOI: 10.1021/ar00143a004

Photoinduced Reconfiguration Cycle in a Molecular Adsorbate Layer Studied by Femtosecond Inner-Shell Photoelectron Spectroscopy
journal, March 2011


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

    Works referencing / citing this record:

    Time-resolved electron spectroscopy for chemical analysis of photodissociation: Photoelectron spectra of Fe(CO)$_5$ , Fe(CO)$_4$ , and Fe(CO)$_3$
    text, January 2018