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

Shiery, Richard C.; Fulton, John L.; Balasubramanian, Mahalingam; Nguyen, Manh-Thuong; Lu, Jun-Bo; Li, Jun; Rousseau, Roger; Glezakou, Vassiliki-Alexandra; Cantu, David C.

doi:10.1021/acs.inorgchem.0c03438

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

Journal Article · Fri Feb 05 00:00:00 EST 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c03438· OSTI ID:1769883

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Univ. of Nevada, Reno, NV (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Tsinghua Univ., Beijing (China)

To resolve the fleeting structures of lanthanide Ln³⁺ aqua ions in solution, we (i) performed the first ab initio molecular dynamics (AIMD) simulations of the entire series of Ln³⁺ 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 Ln³⁺ 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. In this study, we performed a comprehensive evaluation of EXAFS multiple-scattering analysis (up to 6.5 Å) 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 L₃- and L₁-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 Å 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 Ln³⁺ aqua ions.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830; AC02-06CH11357

OSTI ID:: 1769883

Alternate ID(s):: OSTI ID: 1777364

Report Number(s):: PNNL-SA-155623

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 5; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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