التفاصيل البيبلوغرافية
| العنوان: |
Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X‑ray Absorption Spectroscopy |
| المؤلفون: |
Richard C. Shiery (10104507), John L. Fulton (1280817), Mahalingam Balasubramanian (1280823), Manh-Thuong Nguyen (1675864), Jun-Bo Lu (2562907), Jun Li (6494), Roger Rousseau (1288167), Vassiliki-Alexandra Glezakou (1337457), David C. Cantu (3704377) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Medicine, Plant Biology, Computational Biology, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, hydrating waters, Ab Initio Molecular Dynamics, AIMD trajectories, L 1, AIMD simulations, Coordination Sphere, hydration shell, EXAFS spectra, EXAFS multiple-scattering analysis, aqua, coordination geometry, EXAFS data, Lanthanide Aqua Ions, lanthanide, symmetry-dependent L 3, 0.07 Å, Ln, basis sets, X-ray absorption, coordination shell, ab initio |
| الوصف: |
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 (Nd 3+ , Dy 3+ , Er 3+ , Lu 3+ ) 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 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 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 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 Ln 3+ aqua ions. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Coordination_Sphere_of_Lanthanide_Aqua_Ions_Resolved_with_Ab_Initio_Molecular_Dynamics_and_X_ray_Absorption_Spectroscopy/13721820 |
| DOI: |
10.1021/acs.inorgchem.0c03438.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.inorgchem.0c03438.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.7EA4AF5C |
| قاعدة البيانات: |
BASE |