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

Abstract

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 include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra and Fe 1s core hole spectra using X-ray absorption and emission techniques. These experiments are accompanied by density functional theory (DFT) based quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations and spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. Our simulations, including explicit solvent effects, across this large energy window allows for a systematic comparison of vibrational, valence electronic and core-level spectra. The analysis reveals how the local solvation environment influences the geometric and electronic structure and impacts the line shape and intensity of the observed spectral features in the infrared, optical and X-ray wavelengths.

Authors:
ORCiD logo [1];  [2];  [1];  [3]; ; ; ;  [4];  [4];  [4]; ; ; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, University of Washington, Seattle, Washington 98115, United States
  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
  3. Department of Chemistry, Physics and Astronomy, University of California, Irvine, California 92697, United States
  4. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1489803
Report Number(s):
PNNL-SA-131330
Journal ID: ISSN 1520-6106
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
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
Country of Publication:
United States
Language:
English

Citation Formats

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., 2018. 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. Tue . "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.
@article{osti_1489803,
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 = {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 include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra and Fe 1s core hole spectra using X-ray absorption and emission techniques. These experiments are accompanied by density functional theory (DFT) based quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations and spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. Our simulations, including explicit solvent effects, across this large energy window allows for a systematic comparison of vibrational, valence electronic and core-level spectra. The analysis reveals how the local solvation environment influences the geometric and electronic structure and impacts the line shape and intensity of the observed spectral features in the infrared, optical and X-ray wavelengths.},
doi = {10.1021/acs.jpcb.7b12532},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 19,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}