Hydration of divalent lanthanides, Sm2+ and Eu2+ : A molecular dynamics study with polarizable AMOEBA force field. 2022

Hesam Arabzadeh, and Chengwen Liu, and Orlando Acevedo, and Pengyu Ren, and Wei Yang, and Thomas Albrecht-Schönzart
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida, USA.

The chemistry of divalent lanthanides, Ln2+ , is a growing sub-field of heavy element chemistry owing to new synthetic approaches. However, some theoretical aspects of these unusual cations are currently underdeveloped, especially as they relate to their dynamic properties in solution. In this work, we address the hydration of two of the classical Ln2+ cations, Sm2+ and Eu2+ , using atomic multipole optimized energetic for biomolecular applications (AMOEBA) force fields. These cations have not been parameterized to date with AMOEBA, and few studies are available because of their instability with respect to oxidation in aqueous media. Coordination numbers (CN's) of 8.2 and 8.1 respectively for Sm2+ and Eu2+ , and 8.8 for both Sm3+ and Eu3+ have been obtained and are in good agreement with the few available AIMD and X-ray absorption fine structures studies. The decreased CN of Ln2+ compared with Ln3+ arises from progressive water exchange events that indicates the gradual stabilization of 8-coordinate structures with respect to 9-coordinate geometries. Moreover, the effects of the chloride counter anions on the coordination of Ln2+ cations have been studied at different chloride concentrations in this work. Lastly, water exchange times of Ln2+ cations have been calculated to provide a comprehensive understanding of the behavior of Eu2+ and Sm2+ in aqueous chloride media.

UI MeSH Term Description Entries
D002412 Cations Positively charged atoms, radicals or groups of atoms which travel to the cathode or negative pole during electrolysis. Cation
D002712 Chlorides Inorganic compounds derived from hydrochloric acid that contain the Cl- ion. Chloride,Chloride Ion Level,Ion Level, Chloride,Level, Chloride Ion
D000656 Amoeba A genus of ameboid protozoa. Characteristics include a vesicular nucleus and the formation of several PSEUDOPODIA, one of which is dominant at a given time. Reproduction occurs asexually by binary fission. Ameba
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide
D056004 Molecular Dynamics Simulation A computer simulation developed to study the motion of molecules over a period of time. Molecular Dynamics Simulations,Molecular Dynamics,Dynamic, Molecular,Dynamics Simulation, Molecular,Dynamics Simulations, Molecular,Dynamics, Molecular,Molecular Dynamic,Simulation, Molecular Dynamics,Simulations, Molecular Dynamics
D028581 Lanthanoid Series Elements Elements of the lanthanoid series including atomic number 57 (LANTHANUM) through atomic number 71 (LUTETIUM). Lanthanide,Lanthanides,Lanthanoid,Lanthanoids,Elements, Lanthanoid Series

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