4.5 Article

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

Journal

JOURNAL OF PHYSICAL CHEMISTRY B
Volume 122, Issue 19, Pages 5075-5086

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.7b12532

Keywords

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Funding

  1. DOE Office of Science User Facility [DE-AC02-05CH11231]
  2. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0012450, DE-FG02-04ER15571, KC-030105066418]
  3. Office of Biological and Environmental Research
  4. United States Department of Energy under DOE [DE-AC05-76RL1830]
  5. Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
  6. U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences through Argonne National Laboratory (ANL)
  7. U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences through Lawrence Berkeley National Laboratory (LBNL)
  8. DOE Office of Science [DE-AC02-06CH11357]

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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 Is core hole spectra using element-specificresonant 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. Athough 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.

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