4.7 Article

Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 5, Pages 3117-3130

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03438

Keywords

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Funding

  1. American Chemical Society Petroleum Research Fund
  2. U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [72353, 16248]
  3. U.S. DOE [DE-AC05-76RL01830]
  4. DOE Office of Science [DE-AC02-06CH11357]
  5. National Natural Science Foundation of China [22033005]
  6. Guangdong Provincial Key Laboratory of Catalysis [2020B121201002]

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By utilizing first-principles molecular dynamics simulations and extended X-ray absorption fine structure experiments, we were able to measure the symmetry of hydrating waters around lanthanide Ln(3+) aqua ions, revealing a dynamically symmetrically disordered first coordination shell characteristic of most lanthanides.
To resolve the fleeting structures of lanthanide Ln(3+) aqua ions in solution, we (i) performed the first ab initio molecular dynamics (AIMD) simulations of the entire series of Ln(3+) aqua ions in explicit water solvent using pseudopotentials and basis sets recently optimized for lanthanides and (ii) measured the symmetry of the hydrating waters about Ln(3+) ions (Nd3+, Dy3+, Er3+, Lu3+) for the first time with extended X-ray absorption fine structure (EXAFS). EXAFS spectra were measured experimentally and generated from AIMD trajectories to directly compare simulation, which concurrently considers the electronic structure and the atomic dynamics in solution, with experiment. We performed a comprehensive evaluation of EXAFS multiple-scattering analysis (up to 6.5 angstrom) to measure Ln-O distances and angular correlations (i.e., symmetry) and elucidate the molecular geometry of the first hydration shell. This evaluation, in combination with symmetry-dependent L-3- and L-1-edge spectral analysis, shows that the AIMD simulations remarkably reproduces the experimental EXAFS data. The error in the predicted Ln-O distances is less than 0.07 angstrom for the later lanthanides, while we observed excellent agreement with predicted distances within experimental uncertainty for the early lanthanides. Our analysis revealed a dynamic, symmetrically disordered first coordination shell, which does not conform to a single molecular geometry for most lanthanides. This work sheds critical light on the highly elusive coordination geometry of the Ln(3+) aqua ions.

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