Molecular dynamics simulations of Eu(NO3)3 salt with DMDOHEMA in n-alkanes: Unravelling curvature properties in liquid-liquid extraction

Stemplinger, Simon; Duvail, Magali; Dufrêche, Jean‐François

doi:10.1016/j.molliq.2021.118035

Cited by 4 publications

(3 citation statements)

References 76 publications

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“…Here, for the n -heptane and DMDOHEMA molecules, the GAFF2 model was used for intramolecular interactions. , For DMDOHEMA molecules, we used the same 12-6 LJ parameters as in our previous study, except for the aliphatic carbon (type CT) and hydrogen (type HC) atoms, which were modeled using the long-hydrocarbon model developed by Siu et al This model was also used for the n -heptane molecules as already done in previous works. , Partial atomic charges on n -heptane were recalculated from our previous polarizable model not considering the polarization, i.e., the 0.8 rescaling factor was not applied (Figure S8). For DMDOHEMA, the partial atomic charges are those already used in our previous polarizable model (Figure S1 of ref ).…”

Section: Results and Discussionmentioning

confidence: 99%

Modeling Lanthanide Ions in Solution: A Versatile Force Field in Aqueous and Organic Solvents

Duvail,

Moreno Martinez,

Žiberna

et al. 2024

J. Chem. Theory Comput.

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In this paper, we propose a new nonpolarizable force field for describing the Ln 3+ (Ln = lanthanide) series based on a 12-6-4 Lennard-Jones potential. The development of the force field was performed in pure water by adjusting both the ion−oxygen distance and the hydration free energy. This force field accurately reproduces the Ln 3+ hydration properties through the series, especially the coordination number that is hardly accessible using a nonpolarizable force field. Then, the validity and the transferability of the current force field were evaluated for two different systems containing Ln 3+ in various solvents, namely, 0.1 mol L −1 La(NO 3 ) 3 salts in methanol and Eu(NO 3 ) 3 salts in solvent organic phases composed of DMDOHEMA molecules in n-heptane. The good agreement between our simulations and the data available in the literature confirms the accuracy of the force field for describing the lanthanide cations in both aqueous and nonaqueous media.

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Section: Results and Discussionmentioning

confidence: 99%

Modeling Lanthanide Ions in Solution: A Versatile Force Field in Aqueous and Organic Solvents

Duvail,

Moreno Martinez,

Žiberna

et al. 2024

J. Chem. Theory Comput.

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“…Diglycolamides tend to form 3:1 ligand-to-metal complexes with Ln(III) ions, 48 leading to a total CN of 9, where nitrates are found to be not present in the first coordination sphere; this is supported by both extended X-ray absorption fine structure (EXAFS) 49 and single-crystal X-ray diffraction. 50 In the case of the bidentate malonamides, classical MD simulations showed that three nitrates are coordinated to Eu(III) in the first coordination shell of the 3:1 complex, 51 and EXAFS data suggested that they are about half monodentate and half bidentate. 52 This scenario resembles our 2:1 complex case where nitrates can dynamically switch between monodentate or bidentate.…”

Section: Resultsmentioning

confidence: 99%

Atomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase

et al. 2022

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Rare-earth elements (REEs) such as neodymium are critical materials needed in many important technologies, and rigid neutral bis-lactam-1,10-phenanthroline (BLPhen) ligands show one of the highest extraction performance for complexing Nd(III) in REE uptake and separation processes. However, the local structure of the complexes formed between BLPhen and Nd(III) in a typical organic solvent such as dichloroethane (DCE) is unclear. Here, we perform first-principles molecular dynamics (FPMD) simulations to unveil the structure of complexes formed by BLPhen with Nd(NO 3 ) 3 in the DCE solvent. BLPhen can bind to Nd(III) in either 1:1 or 2:1 fashion. In the 1:1 complex, three nitrates bind to Nd(III) via the bidentate mode in the first solvation shell, leading to the formation of a neutral complex, [Nd(BLPhen)(NO 3 ) 3 ] 0 , in the organic phase. In contrast, there are two nitrates in the first solvation shell in the 2:1 complex, creating a charged complex, [Nd(BLPhen) 2 (NO 3 ) 2 ] + . The third nitrate was found to be far away from the metal center, migrating to the outer solvation shell. Our simulations show that the binding pocket formed by the two rigid BLPhen ligands allows ample space for two nitrates to bind to the Nd(III) center from opposite sides. Our findings of two nitrates in the first solvation shell of the 2:1 complex and the corresponding bond distances agree well with the available crystal structure. This study represents the first accurate FPMD modeling of the BLPhen–Nd(III) complexes in an explicit organic solvent and opens the door to more atomistic understanding of REE separations from first principles.

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“…This was also performed in the case of water-poor reverse aggregates. 55 The surfactant movement as a minor protrusion is only apparent in the case of micelles, while positions are more reminiscent of a diffuse cloud in the case of short chain amphiphiles approximating the weak aggregation characteristic of hydrotropes.…”

Section: Discussionmentioning

confidence: 99%

Short-chain branched sulfosuccinate as a missing link between surfactants and hydrotropes

Stemplinger

Causse

Prévost

et al. 2022

Phys. Chem. Chem. Phys.

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Molecular dynamics simulations of Eu(NO3)3 salt with DMDOHEMA in n-alkanes: Unravelling curvature properties in liquid-liquid extraction

Cited by 4 publications

References 76 publications

Modeling Lanthanide Ions in Solution: A Versatile Force Field in Aqueous and Organic Solvents

Modeling Lanthanide Ions in Solution: A Versatile Force Field in Aqueous and Organic Solvents

Atomistic Insights into Structure and Dynamics of Neodymium(III) Complexation with a Bis-lactam Phenanthroline Ligand in the Organic Phase

Short-chain branched sulfosuccinate as a missing link between surfactants and hydrotropes

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