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Title: Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency

Abstract

Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron–ruthenium complex, [(CN)5FeIICNRuIII(NH3)5]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ~ 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.

Authors:
 [1];  [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5];  [1];  [4]; ORCiD logo [1];  [4]; ORCiD logo [6];  [7];  [6];  [1];  [5];  [7];  [8]; ORCiD logo [9]; ORCiD logo [9];  [9] more »; ORCiD logo [8]; ORCiD logo [5];  [10]; ORCiD logo [11]; ORCiD logo [1] « less
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Technical Univ. of Denmark, Lyngby (Denmark)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  8. Univ. of California, Irvine, CA (United States)
  9. Argonne National Lab. (ANL), Argonne, IL (United States)
  10. 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)
  11. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1840028
Alternate Identifier(s):
OSTI ID: 1863237; OSTI ID: 1959972
Grant/Contract Number:  
AC02-06CH11357; AC02-76SF00515; FG02-04ER15571; SC0012450; SC0019277; KC-030105066418; KC-030105172685; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 13; Journal Issue: 1; 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

Liekhus-Schmaltz, Chelsea, Fox, Zachary W., Andersen, Amity, Kjaer, Kasper S., Alonso-Mori, Roberto, Biasin, Elisa, Carlstad, Julia, Chollet, Matthieu, Gaynor, James D., Glownia, James M., Hong, Kiryong, Kroll, Thomas, Lee, Jae Hyuk, Poulter, Benjamin I., Reinhard, Marco, Sokaras, Dimosthenis, Zhang, Yu, Doumy, Gilles, March, Anne Marie, Southworth, Stephen H., Mukamel, Shaul, Cordones, Amy A., Schoenlein, Robert W., Govind, Niranjan, and Khalil, Munira. Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency. United States: N. p., 2022. Web. doi:10.1021/acs.jpclett.1c03613.
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Liekhus-Schmaltz, Chelsea, Fox, Zachary W., Andersen, Amity, Kjaer, Kasper S., Alonso-Mori, Roberto, Biasin, Elisa, Carlstad, Julia, Chollet, Matthieu, Gaynor, James D., Glownia, James M., Hong, Kiryong, Kroll, Thomas, Lee, Jae Hyuk, Poulter, Benjamin I., Reinhard, Marco, Sokaras, Dimosthenis, Zhang, Yu, Doumy, Gilles, March, Anne Marie, Southworth, Stephen H., Mukamel, Shaul, Cordones, Amy A., Schoenlein, Robert W., Govind, Niranjan, & Khalil, Munira. Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency. United States. https://doi.org/10.1021/acs.jpclett.1c03613
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Liekhus-Schmaltz, Chelsea, Fox, Zachary W., Andersen, Amity, Kjaer, Kasper S., Alonso-Mori, Roberto, Biasin, Elisa, Carlstad, Julia, Chollet, Matthieu, Gaynor, James D., Glownia, James M., Hong, Kiryong, Kroll, Thomas, Lee, Jae Hyuk, Poulter, Benjamin I., Reinhard, Marco, Sokaras, Dimosthenis, Zhang, Yu, Doumy, Gilles, March, Anne Marie, Southworth, Stephen H., Mukamel, Shaul, Cordones, Amy A., Schoenlein, Robert W., Govind, Niranjan, and Khalil, Munira. Wed . "Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency". United States. https://doi.org/10.1021/acs.jpclett.1c03613. https://www.osti.gov/servlets/purl/1840028.
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@article{osti_1840028,
title = {Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency},
author = {Liekhus-Schmaltz, Chelsea and Fox, Zachary W. and Andersen, Amity and Kjaer, Kasper S. and Alonso-Mori, Roberto and Biasin, Elisa and Carlstad, Julia and Chollet, Matthieu and Gaynor, James D. and Glownia, James M. and Hong, Kiryong and Kroll, Thomas and Lee, Jae Hyuk and Poulter, Benjamin I. and Reinhard, Marco and Sokaras, Dimosthenis and Zhang, Yu and Doumy, Gilles and March, Anne Marie and Southworth, Stephen H. and Mukamel, Shaul and Cordones, Amy A. and Schoenlein, Robert W. and Govind, Niranjan and Khalil, Munira},
abstractNote = {Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron–ruthenium complex, [(CN)5FeIICNRuIII(NH3)5]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ~ 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.},
doi = {10.1021/acs.jpclett.1c03613},
journal = {Journal of Physical Chemistry Letters},
number = 1,
volume = 13,
place = {United States},
year = {Wed Jan 05 00:00:00 EST 2022},
month = {Wed Jan 05 00:00:00 EST 2022}
}
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