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Title: Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy

Abstract

Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. Here, we extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN)2n(2, 2'-bipyridine)3-n]-2n+2, n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [2];  [5];  [5]; ORCiD logo [5];  [5]; ORCiD logo [6];  [6];  [2];  [2]; ORCiD logo [7];  [5]
  1. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  3. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  6. Technical Univ. of Denmark, Lyngby (Denmark)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1608797
Alternate Identifier(s):
OSTI ID: 1600586
Grant/Contract Number:  
SCW0063; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 7; 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

Ledbetter, Kathryn, Reinhard, Marco E., Kunnus, Kristjan, Gallo, Alessandro, Britz, Alexander, Biasin, Elisa, Glownia, James M., Nelson, Silke, Van Driel, Tim B., Weninger, Clemens, Zederkof, Diana B., Haldrup, Kristoffer, Cordones, Amy A., Gaffney, Kelly J., Sokaras, Dimosthenis, and Alonso-Mori, Roberto. Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy. United States: N. p., 2020. Web. https://doi.org/10.1063/1.5139441.
Ledbetter, Kathryn, Reinhard, Marco E., Kunnus, Kristjan, Gallo, Alessandro, Britz, Alexander, Biasin, Elisa, Glownia, James M., Nelson, Silke, Van Driel, Tim B., Weninger, Clemens, Zederkof, Diana B., Haldrup, Kristoffer, Cordones, Amy A., Gaffney, Kelly J., Sokaras, Dimosthenis, & Alonso-Mori, Roberto. Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy. United States. https://doi.org/10.1063/1.5139441
Ledbetter, Kathryn, Reinhard, Marco E., Kunnus, Kristjan, Gallo, Alessandro, Britz, Alexander, Biasin, Elisa, Glownia, James M., Nelson, Silke, Van Driel, Tim B., Weninger, Clemens, Zederkof, Diana B., Haldrup, Kristoffer, Cordones, Amy A., Gaffney, Kelly J., Sokaras, Dimosthenis, and Alonso-Mori, Roberto. Fri . "Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy". United States. https://doi.org/10.1063/1.5139441. https://www.osti.gov/servlets/purl/1608797.
@article{osti_1608797,
title = {Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy},
author = {Ledbetter, Kathryn and Reinhard, Marco E. and Kunnus, Kristjan and Gallo, Alessandro and Britz, Alexander and Biasin, Elisa and Glownia, James M. and Nelson, Silke and Van Driel, Tim B. and Weninger, Clemens and Zederkof, Diana B. and Haldrup, Kristoffer and Cordones, Amy A. and Gaffney, Kelly J. and Sokaras, Dimosthenis and Alonso-Mori, Roberto},
abstractNote = {Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. Here, we extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN)2n(2, 2'-bipyridine)3-n]-2n+2, n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps.},
doi = {10.1063/1.5139441},
journal = {Journal of Chemical Physics},
number = 7,
volume = 152,
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy
journal, January 2017

  • March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina
  • The Journal of Physical Chemistry C, Vol. 121, Issue 5
  • DOI: 10.1021/acs.jpcc.6b12940

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

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

Ultrafast events in the electron photodetachment from the hexacyanoferrate(II) complex in solution
journal, May 1998

  • Pommeret, Stanislas; Naskrecki, Ryszard; van der Meulen, Peter
  • Chemical Physics Letters, Vol. 288, Issue 5-6
  • DOI: 10.1016/s0009-2614(98)00371-6

Insights into the Geometric and Electronic Structure of Transition Metal Centers from Valence-to-Core X-ray Emission Spectroscopy
journal, September 2015


Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy
journal, July 2010

  • Lee, Nicole; Petrenko, Taras; Bergmann, Uwe
  • Journal of the American Chemical Society, Vol. 132, Issue 28
  • DOI: 10.1021/ja101281e

Valence-to-Core X-Ray Emission Spectroscopy of Iron-Carbonyl Complexes: Implications for the Examination of Catalytic Intermediates
journal, October 2013

  • Delgado-Jaime, Mario Ulises; DeBeer , Serena; Bauer, Matthias
  • Chemistry - A European Journal, Vol. 19, Issue 47
  • DOI: 10.1002/chem.201301913

Achieving few-femtosecond time-sorting at hard X-ray free-electron lasers
journal, February 2013


Pump–probe experimental methodology at the Linac Coherent Light Source
journal, April 2019

  • Glownia, James M.; Gumerlock, Karl; Lemke, Henrik T.
  • Journal of Synchrotron Radiation, Vol. 26, Issue 3
  • DOI: 10.1107/s160057751900225x

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2′-bipyridine) 2 (CN) 2 ]
journal, July 2017

  • Kjær, Kasper S.; Zhang, Wenkai; Alonso-Mori, Roberto
  • Structural Dynamics, Vol. 4, Issue 4
  • DOI: 10.1063/1.4985017

Development of high-repetition-rate laser pump/x-ray probe methodologies for synchrotron facilities
journal, July 2011

  • March, Anne Marie; Stickrath, Andrew; Doumy, Gilles
  • Review of Scientific Instruments, Vol. 82, Issue 7
  • DOI: 10.1063/1.3615245

Tracking excited-state charge and spin dynamics in iron coordination complexes
journal, May 2014

  • Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe
  • Nature, Vol. 509, Issue 7500
  • DOI: 10.1038/nature13252

Excited State Chemistry of the Ferrocyanide Ion in Aqueous Solution. II. Photoaquation
journal, October 1971

  • Shirom, Miriam; Stein, Gabriel
  • The Journal of Chemical Physics, Vol. 55, Issue 7
  • DOI: 10.1063/1.1676588

Excited State Chemistry of the Ferrocyanide Ion in Aqueous Solution. I. Formation of the Hydrated Electron
journal, October 1971

  • Shirom, Miriam; Stein, Gabriel
  • The Journal of Chemical Physics, Vol. 55, Issue 7
  • DOI: 10.1063/1.1676587

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses
journal, March 2015

  • Canton, Sophie E.; Kjær, Kasper S.; Vankó, György
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7359

A multi-crystal wavelength dispersive x-ray spectrometer
journal, July 2012

  • Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis
  • Review of Scientific Instruments, Vol. 83, Issue 7
  • DOI: 10.1063/1.4737630

Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy
journal, June 2017


Valence to Core X-ray Emission Spectroscopy
journal, May 2014


Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species
journal, February 2015

  • March, Anne Marie; Assefa, Tadesse A.; Bressler, Christian
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/jp511838q

Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998

  • Barone, Vincenzo; Cossi, Maurizio
  • The Journal of Physical Chemistry A, Vol. 102, Issue 11
  • DOI: 10.1021/jp9716997

High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005


Software update: the ORCA program system, version 4.0: Software update
journal, July 2017

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1
  • DOI: 10.1002/wcms.1327

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

The X-ray Correlation Spectroscopy instrument at the Linac Coherent Light Source
journal, April 2015

  • Alonso-Mori, Roberto; Caronna, Chiara; Chollet, Matthieu
  • Journal of Synchrotron Radiation, Vol. 22, Issue 3
  • DOI: 10.1107/s1600577515004397

Simultaneous Femtosecond X-ray Spectroscopy and Diffraction of Photosystem II at Room Temperature
journal, February 2013


Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2′-bipyridine)(CN) 4 ] 2−
journal, January 2018

  • Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 6
  • DOI: 10.1039/C7CP07838B

Low-Spin versus High-Spin Ground State in Pseudo-Octahedral Iron Complexes
journal, May 2012

  • Bowman, David N.; Jakubikova, Elena
  • Inorganic Chemistry, Vol. 51, Issue 11
  • DOI: 10.1021/ic202344w

Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand
journal, April 2011

  • Pollock, Christopher J.; DeBeer, Serena
  • Journal of the American Chemical Society, Vol. 133, Issue 14
  • DOI: 10.1021/ja200560z

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution
journal, January 2017

  • Zhang, Wenkai; Kjær, Kasper S.; Alonso-Mori, Roberto
  • Chemical Science, Vol. 8, Issue 1
  • DOI: 10.1039/c6sc03070j

Density functional calculations of molecular hyperfine interactions in the zero order regular approximation for relativistic effects
journal, March 1998

  • van Lenthe, Erik; van der Avoird, Ad; Wormer, Paul E. S.
  • The Journal of Chemical Physics, Vol. 108, Issue 12
  • DOI: 10.1063/1.475889

Sensitivity of X-ray Core Spectroscopy to Changes in Metal Ligation: A Systematic Study of Low-Coordinate, High-Spin Ferrous Complexes
journal, May 2013

  • Chandrasekaran, P.; Chiang, Karen P.; Nordlund, Dennis
  • Inorganic Chemistry, Vol. 52, Issue 11
  • DOI: 10.1021/ic3021723

Micro-focused MHz pink beam for time-resolved X-ray emission spectroscopy
journal, October 2019

  • Tu, Ming-Feng; Doumy, Gilles; Al Haddad, Andre
  • Journal of Synchrotron Radiation, Vol. 26, Issue 6
  • DOI: 10.1107/S1600577519012268

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity
journal, October 2019

  • March, Anne Marie; Doumy, Gilles; Andersen, Amity
  • The Journal of Chemical Physics, Vol. 151, Issue 14
  • DOI: 10.1063/1.5117318