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.
Ross, Matthew, et al. "Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths." Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, vol. 122, no. 19, Apr. 2018. https://doi.org/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 (2018). Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths. Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, 122(19). https://doi.org/10.1021/acs.jpcb.7b12532
Ross, Matthew, Andersen, Amity, Fox, Zachary W., et al., "Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths," Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry 122, no. 19 (2018), https://doi.org/10.1021/acs.jpcb.7b12532
@article{osti_1489803,
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 others},
title = {Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths},
annote = {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},
url = {https://www.osti.gov/biblio/1489803},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {ISSN 1520-6106},
number = {19},
volume = {122},
place = {United States},
publisher = {American Chemical Society},
year = {2018},
month = {04}}
PROCEEDINGS OF THE 12TH INTERNATIONAL CONFERENCE ON SYNCHROTRON RADIATION INSTRUMENTATION – SRI2015, AIP Conference Proceedingshttps://doi.org/10.1063/1.4952871