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Title: Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths

Here, we present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute–solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute–solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute–solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis,more » X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute–solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.« less
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [6] ;  [7] ;  [8] ;  [8] ;  [8] ;  [9] ;  [7] ; ORCiD logo [10] ; ORCiD logo [2] ; ORCiD logo [3]
  1. Univ. of Washington, Seattle, WA (United States); Corning Inc., Corning, NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Univ. of Washington, Seattle, WA (United States)
  4. Univ. of California, Irvine, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Korea Research Institute of Standards and Science, Daejeon (Republic of Korea)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pohang Accelerator Lab., Kyungbuk (Republic of Korea)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  8. Argonne National Lab. (ANL), Argonne, IL (United States)
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  10. Univ. of California, Irvine, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 19; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1461346

Ross, Matthew, Andersen, Amity, Fox, Zachary W., Zhang, Yu, Hong, Kiryong, Lee, Jae -Hyuk, Cordones, Amy, March, Anne Marie, Doumy, Gilles, Southworth, Stephen H., Marcus, Matthew A., Schoenlein, Robert W., Mukamel, Shaul, Govind, Niranjan, and Khalil, Munira. Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths. United States: N. p., Web. doi:10.1021/acs.jpcb.7b12532.
Ross, Matthew, Andersen, Amity, Fox, Zachary W., Zhang, Yu, Hong, Kiryong, Lee, Jae -Hyuk, Cordones, Amy, March, Anne Marie, Doumy, Gilles, Southworth, Stephen H., Marcus, Matthew A., Schoenlein, Robert W., Mukamel, Shaul, Govind, Niranjan, & Khalil, Munira. Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths. United States. doi:10.1021/acs.jpcb.7b12532.
Ross, Matthew, Andersen, Amity, Fox, Zachary W., Zhang, Yu, Hong, Kiryong, Lee, Jae -Hyuk, Cordones, Amy, March, Anne Marie, Doumy, Gilles, Southworth, Stephen H., Marcus, Matthew A., Schoenlein, Robert W., Mukamel, Shaul, Govind, Niranjan, and Khalil, Munira. 2018. "Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths". United States. doi:10.1021/acs.jpcb.7b12532. https://www.osti.gov/servlets/purl/1461346.
@article{osti_1461346,
title = {Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths},
author = {Ross, Matthew and Andersen, Amity and Fox, Zachary W. and Zhang, Yu and Hong, Kiryong and Lee, Jae -Hyuk and Cordones, Amy and March, Anne Marie and Doumy, Gilles and Southworth, Stephen H. and Marcus, Matthew A. and Schoenlein, Robert W. and Mukamel, Shaul and Govind, Niranjan and Khalil, Munira},
abstractNote = {Here, we present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute–solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute–solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute–solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute–solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.},
doi = {10.1021/acs.jpcb.7b12532},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 19,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}