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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];  [7];  [6];  [6];  [8]; ORCiD logo [6];  [6];  [9];  [10]; ORCiD logo [11] more »; ORCiD logo [4];  [6]; ORCiD logo [2];  [3] « less
  1. Univ. Potsdam, Potsdam (Germany)
  2. Stockholm Univ., Stockholm (Sweden)
  3. Univ. Potsdam, Potsdam (Germany); Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  4. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  5. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Warwick, Coventry (United Kingdom)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States); Beijing Normal Univ., Beijing (China)
  9. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); European XFEL, Schenefeld (Germany)
  10. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Gottingen Univ., Gottingen (Germany)
  11. Uppsala Univ., Uppsala (Sweden); Univ. di Siena, Siena (Italy)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters; 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, Kubicek, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, and Fohlisch, 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.
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, Kubicek, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, & Fohlisch, Alexander. Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering. United States. doi:10.1021/acs.jpclett.8b01429.
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, Kubicek, Katharina, Techert, Simone A., Lundberg, Marcus, Wernet, Philippe, Gaffney, Kelly, Odelius, Michael, and Fohlisch, Alexander. Mon . "Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering". United States. doi:10.1021/acs.jpclett.8b01429.
@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 Kubicek, Katharina and Techert, Simone A. and Lundberg, Marcus and Wernet, Philippe and Gaffney, Kelly and Odelius, Michael and Fohlisch, 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 = ,
volume = ,
place = {United States},
year = {Mon Jun 11 00:00:00 EDT 2018},
month = {Mon Jun 11 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.jpclett.8b01429

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