Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

Abstract

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5];  [4];  [4];  [6];  [6];  [6];  [6];  [6];  [6];  [7];  [7]; ORCiD logo [7];  [7];  [8];  [9]; ORCiD logo [10] more »; ORCiD logo [4];  [7]; ORCiD logo [2];  [3] « less
+ Show Author Affiliations
  1. Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany
  2. Department of Physics, Stockholm University, Albanova University Center, 10691 Stockholm, Sweden
  3. Institut für Physik und Astronomie, Universität Potsdam, 14476 Potsdam, Germany, Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
  4. Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany
  5. Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 12489 Berlin, Germany, DESY Photon Science, 22607 Hamburg, Germany
  6. LCLS, SLAC, Menlo Park, California 94025, United States
  7. PULSE Institute, SLAC, Menlo Park, California 94025, United States
  8. DESY Photon Science, 22607 Hamburg, Germany
  9. DESY Photon Science, 22607 Hamburg, Germany, Institute for X-ray Physics, Göttingen University, 37077 Göttingen, Germany
  10. Department of Chemistry - Ȧngström Laboratory, Uppsala University, 75121 Uppsala, Sweden, Department of Biotechnology, Chemistry and Pharmacy, Università di Siena, 53100 Siena, Italy
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1457798
Alternate Identifier(s):
OSTI ID: 1454547
Report Number(s):
SLAC-PUB-17249
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
VI419; SFB 755; SB755 (B03); KAW-2013.0020; 87008; 669531; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters Journal Volume: 9 Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jay, Raphael M., Norell, Jesper, Eckert, Sebastian, Hantschmann, Markus, Beye, Martin, Kennedy, Brian, Quevedo, Wilson, Schlotter, William F., Dakovski, Georgi L., Minitti, Michael P., Hoffmann, Matthias C., Mitra, Ankush, Moeller, Stefan P., Nordlund, Dennis, Zhang, Wenkai, Liang, Huiyang W., Kunnus, Kristjan, Kubiček, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, and Föhlisch, Alexander. Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b01429.
Copy to clipboard
Jay, Raphael M., Norell, Jesper, Eckert, Sebastian, Hantschmann, Markus, Beye, Martin, Kennedy, Brian, Quevedo, Wilson, Schlotter, William F., Dakovski, Georgi L., Minitti, Michael P., Hoffmann, Matthias C., Mitra, Ankush, Moeller, Stefan P., Nordlund, Dennis, Zhang, Wenkai, Liang, Huiyang W., Kunnus, Kristjan, Kubiček, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, & Föhlisch, Alexander. Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering. United States. https://doi.org/10.1021/acs.jpclett.8b01429
Copy to clipboard
Jay, Raphael M., Norell, Jesper, Eckert, Sebastian, Hantschmann, Markus, Beye, Martin, Kennedy, Brian, Quevedo, Wilson, Schlotter, William F., Dakovski, Georgi L., Minitti, Michael P., Hoffmann, Matthias C., Mitra, Ankush, Moeller, Stefan P., Nordlund, Dennis, Zhang, Wenkai, Liang, Huiyang W., Kunnus, Kristjan, Kubiček, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, and Föhlisch, Alexander. Mon . "Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering". United States. https://doi.org/10.1021/acs.jpclett.8b01429.
Copy to clipboard
@article{osti_1457798,
title = {Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering},
author = {Jay, Raphael M. and Norell, Jesper and Eckert, Sebastian and Hantschmann, Markus and Beye, Martin and Kennedy, Brian and Quevedo, Wilson and Schlotter, William F. and Dakovski, Georgi L. and Minitti, Michael P. and Hoffmann, Matthias C. and Mitra, Ankush and Moeller, Stefan P. and Nordlund, Dennis and Zhang, Wenkai and Liang, Huiyang W. and Kunnus, Kristjan and Kubiček, Katharina and Techert, Simone A. and Lundberg, Marcus and Wernet, Philippe and Gaffney, Kelly and Odelius, Michael and Föhlisch, Alexander},
abstractNote = {Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.},
doi = {10.1021/acs.jpclett.8b01429},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 9,
place = {United States},
year = {Mon Jun 11 00:00:00 EDT 2018},
month = {Mon Jun 11 00:00:00 EDT 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.8b01429
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 30 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Correspondence between the Oh point group denotation of orbitals of the main manuscript and how orbitals are split into D2h symmetries in the CASPT2 calculations.
All figures and tables (1 total)
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:

A Multispectroscopic Study of 3 d Orbitals in Cobalt Carboxylates: The High Sensitivity of 2p3d Resonant X-ray Emission Spectroscopy to the Ligand Field
journal, December 2012

  • van Schooneveld, Matti M.; Gosselink, Robert W.; Eggenhuisen, Tamara M.
  • Angewandte Chemie International Edition, Vol. 52, Issue 4
  • DOI: 10.1002/anie.201204855

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

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths
journal, April 2018

  • Ross, Matthew; Andersen, Amity; Fox, Zachary W.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 19
  • DOI: 10.1021/acs.jpcb.7b12532

Dynamics of Solvent-Mediated Electron Localization in Electronically Excited Hexacyanoferrate(III)
journal, January 2012

  • Zhang, Wenkai; Ji, Minbiao; Sun, Zheng
  • Journal of the American Chemical Society, Vol. 134, Issue 5
  • DOI: 10.1021/ja207306t

Charge-transfer and impulsive electronic-to-vibrational energy conversion in ferricyanide: ultrafast photoelectron and transient infrared studies
journal, January 2017

  • Ojeda, José; Arrell, Christopher A.; Longetti, Luca
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 26
  • DOI: 10.1039/C7CP03337K

Resonant inelastic x-ray scattering studies of elementary excitations
journal, June 2011

  • Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P.
  • Reviews of Modern Physics, Vol. 83, Issue 2
  • DOI: 10.1103/RevModPhys.83.705

A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources
journal, December 2012

  • Kunnus, Kristjan; Rajkovic, Ivan; Schreck, Simon
  • Review of Scientific Instruments, Vol. 83, Issue 12
  • DOI: 10.1063/1.4772685

Structure and Dynamics of Ferrocyanide and Ferricyanide Anions in Water and Heavy Water: An Insight by MD Simulations and 2D IR Spectroscopy
journal, December 2014

  • Prampolini, Giacomo; Yu, Pengyun; Pizzanelli, Silvia
  • The Journal of Physical Chemistry B, Vol. 118, Issue 51
  • DOI: 10.1021/jp511391b

The soft x-ray instrument for materials studies at the linac coherent light source x-ray free-electron laser
journal, April 2012

  • Schlotter, W. F.; Turner, J. J.; Rowen, M.
  • Review of Scientific Instruments, Vol. 83, Issue 4
  • DOI: 10.1063/1.3698294

Metal–Ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering
journal, October 2013

  • Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja408072q

Second‐order perturbation theory with a complete active space self‐consistent field reference function
journal, January 1992

  • Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O.
  • The Journal of Chemical Physics, Vol. 96, Issue 2
  • DOI: 10.1063/1.462209

Photoaquation Mechanism of Hexacyanoferrate(II) Ions: Ultrafast 2D UV and Transient Visible and IR Spectroscopies
journal, May 2017

  • Reinhard, Marco; Auböck, Gerald; Besley, Nicholas A.
  • Journal of the American Chemical Society, Vol. 139, Issue 21
  • DOI: 10.1021/jacs.7b02769

Electronic structures of hexacyanometalate complexes
journal, July 1968

  • Alexander, John J.; Gray, Harry B.
  • Journal of the American Chemical Society, Vol. 90, Issue 16
  • DOI: 10.1021/ja01018a013

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives
journal, July 2016

  • Kunnus, Kristjan; Zhang, Wenkai; Delcey, Mickaël G.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 29
  • DOI: 10.1021/acs.jpcb.6b04751

Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
journal, October 2016

Ultrafast Independent N−H and N−C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering
journal, April 2017

  • Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.
  • Angewandte Chemie International Edition, Vol. 56, Issue 22
  • DOI: 10.1002/anie.201700239

Restricted active space calculations of L-edge X-ray absorption spectra: From molecular orbitals to multiplet states
journal, September 2014

  • Pinjari, Rahul V.; Delcey, Mickaël G.; Guo, Meiyuan
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896373

Fe L-Edge XAS Studies of K 4 [Fe(CN) 6 ] and K 3 [Fe(CN) 6 ]:  A Direct Probe of Back-Bonding
journal, August 2006

  • Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F.
  • Journal of the American Chemical Society, Vol. 128, Issue 32
  • DOI: 10.1021/ja061802i

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

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

X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions
journal, September 2014

  • Penfold, T. J.; Reinhard, M.; Rittmann-Frank, M. H.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 40
  • DOI: 10.1021/jp5055588

Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species
journal, January 2018

  • Norell, Jesper; Jay, Raphael M.; Hantschmann, Markus
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
  • DOI: 10.1039/C7CP08326B

Light-induced relaxation dynamics of the ferricyanide ion revisited by ultrafast XUV photoelectron spectroscopy
journal, January 2017

  • Engel, Nicholas; Bokarev, Sergey I.; Moguilevski, Alexandre
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 22
  • DOI: 10.1039/C7CP01288H

Measurement of the Ligand Field Spectra of Ferrous and Ferric Iron Chlorides Using 2p3d RIXS
journal, June 2017

Photooxidation and photoaquation of iron hexacyanide in aqueous solution: A picosecond X-ray absorption study
journal, March 2014

  • Reinhard, M.; Penfold, T. J.; Lima, F. A.
  • Structural Dynamics, Vol. 1, Issue 2
  • DOI: 10.1063/1.4871751

Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase
journal, December 2016

  • Godehusen, Kai; Richter, Tobias; Zimmermann, Peter
  • The Journal of Physical Chemistry A, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpca.6b10399

Distorted Tetrahedral Co II in K 5 H[CoW 12 O 40 ]· x H 2 O Probed by 2p3d Resonant Inelastic X-ray Scattering
journal, September 2016

Fe N -Heterocyclic Carbene Complexes as Promising Photosensitizers
journal, July 2016

Valence Photoemission Spectra of Aqueous Fe 2+/3+ and [Fe(CN) 6 ] 4–/3– and Their Interpretation by DFT Calculations
journal, October 2011

  • Seidel, Robert; Thürmer, Stephan; Moens, Jan
  • The Journal of Physical Chemistry B, Vol. 115, Issue 40
  • DOI: 10.1021/jp203997p

Solar Chemistry of Metal Complexes
journal, December 1981

Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands
journal, May 2015

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    Table 1 (p. 5)table
      [ × clear filter / sort ]
      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

      Similar Records in DOE PAGES and OSTI.GOV collections: