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

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.

Molar excess of coordinating N-heterocyclic carbene ligands triggers kinetic digestion of gold nanocrystals.

There has been much interest in evaluating the strength of the coordination interactions between N-heterocyclic carbene (NHC) molecules and transition metal ions, nanocolloids and surfaces. We implement a top-down core digestion test of Au nanoparticles (AuNPs) triggered by incubation with a large molar excess of poly(ethylene glycol)-appended NHC molecules, where kinetic dislodging of surface atoms and formation of NHC-Au complexes progressively take place. We characterize the structure and chemical nature of the generated PEG-NHC-Au complexes using 1D and 2D 1H-13C NMR spectroscopy, supplemented with matrix assisted laser desorption/ionization mass spectrometry, and transmission electron microscopy. We further apply the same test using thiol-modified molecules and find that though etching can be measured the kinetics are substantially slower. We discuss our findings within the classic digestion of transition metal ores and colloids induced by interactions with sodium cyanide, which provides an insight into the strength of coordination between the strong σ-donating (soft Lewis base) NHC and Au surfaces (having a soft Lewis acid character), as compared to gold-to-gold covalent binding.

Free Energy Calculations and Conformational Analysis of Dibenzo-30-crown-10 with Sm2+, Eu2+, and Three Halide Salts in THF Using the AMOEBA Force Field.

Crown ether complexes have been tailored for use in industrial separations of lanthanides (Ln) as a part of rare earth mining and refining. Dibenzo-30-crown-10 (DB30C10) is one of the most efficient complexants for the separation of rare earth mixtures based on the cation size. To understand the origin of this complexation, molecular dynamics (MD) simulations of DB30C10 have been performed using different combinations of divalent Sm and Eu and three halide salts Cl-, Br-, and I- in tetrahydrofuran (THF) solvent. DB30C10 was parameterized here for the polarizable atomic multipole optimized energetics for biomolecular simulation (AMOEBA) force field, and the existing parameters of THF, Sm2+, and Eu2+ were employed from our previous efforts. The large conformational fluctuations present in the DB30C10 systems were found to be dependent both on the identity of the lanthanide and halide complexes. For Cl- and Br- systems, there were no observed conformational changes at 200 ns, while in I- systems, there were two conformational changes with Sm2+ and one with Eu2+ within that same timeframe. In SmI2-DB30C10, there were three stages of conformational changes. In the first stage, the molecule is unfolded, in the second stage, the molecule is partly folded, and finally, in the third stage, the molecule is completely folded. Lastly, the Gibbs binding free energies of DB30C10 with SmBr2 and EuBr2 have been computed, which resulted in nearly identical ΔGcomp values for each lanthanide with Sm2+ being slightly more favorable. Considering the folding mechanism of the SmI2 system with DB30C10, the Gibbs binding free energies of DB30C10 and dicyclohexano-18-crown-6 (DCH18C6) with SmI2 were calculated separately and compared to probe their complexation affinities, in which the former was found to be more favorable.

Molecular Dynamics and Free Energy Calculations of Dicyclohexano-18-crown-6 Diastereoisomers with Sm2+, Eu2+, Dy2+, Yb2+, Cf2+, and Three Halide Salts in Tetrahydrofuran and Acetonitrile Using the AMOEBA Force Field.

With the continual development of lanthanides (Ln) in current technological devices, an efficient separation process is needed that can recover greater amounts of these rare elements. Dicyclohexano-18-crown-6 (DCH18C6) is a crown ether that may be a promising candidate for Ln separation, but additional research is required. As such, molecular dynamics (MD) simulations have been performed on four divalent lanthanide halide salts (Sm2+, Eu2+, Dy2+, and Yb2+) and one divalent actinide halide salt (Cf2+) bound to three diastereoisomers of DCH18C6. Dy2+, Yb2+, Cf2+, DCH18C6, and tetrahydrofuran (THF) solvent were parameterized for the AMOEBA polarizable force field for the first time, whereas existing parameters for Sm2+ and Eu2+ were utilized from our previous efforts. A coordination number (CN) of six for Ln2+/An2+-O solvated in THF indicated that the cations interacted almost entirely with the oxygens of the polyether ring. A CN of one for Ln2+/An2+-N solvated in acetonitrile for systems containing iodide suggested that the N atom of acetonitrile was competitive with I- for cation interactions. Fluctuation between five and six CNs for Dy2+ and Yb2+ suggested that although the cations remained in the polyether ring, the size of the ring may not be an ideal fit as these cations possess comparatively smaller ionic radii. Gibbs binding free energies of Sm2+ in all DCH18C6 diastereoisomers solvated in THF were calculated. The binding free energy of the cis-syn-cis diastereoisomer was the most favorable, followed by cis-anti-cis, and then trans-anti-trans. Finally, two major types of conformation were observed for each diastereoisomer that were related to the electrostatic interactions and charge density of the cations.