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

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [8];  [8];  [9];  [7];  [10];  [2];  [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)
+ Show Author Affiliations
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.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1461346
Alternate ID(s):
OSTI ID: 1530360
OSTI ID: 1489803
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 19 Vol. 122; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Theoretical Analysis of Fe K-Edge XANES on Iron Pentacarbonyl journal March 2020
Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity journal October 2019
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The Effect of Electrolyte Type on the Li Ion Intercalation in Copper Hexacyanoferrate journal January 2019

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