Search results for "solvation"
showing 10 items of 157 documents
Absolute acidity of clay edge sites from ab-initio simulations
2012
International audience; We provide a microscopic understanding of the solvation structure and reactivity of the edges of neutral clays. In particular we address the tendency to deprotonation of the different reactive groups on the (0 1 0) face of pyrophyllite. Such information cannot be inferred directly from titration experiments, which do not discriminate between different sites and whose interpretation resorts to macroscopic models. The determination of the corresponding pKa then usually relies on bond valence models, sometimes improved by incorporating some structural information from ab-initio simulations. Here we use density functional theory based molecular dynamics simulations, comb…
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and elec…
2018
Properties of solid-liquid interfaces are of immense importance for electrocatalytic and electrochemical systems, but modeling such interfaces at the atomic level presents a serious challenge and approaches beyond standard methodologies are needed. An atomistic computational scheme needs to treat at least part of the system quantum mechanically to describe adsorption and reactions, while the entire system is in thermal equilibrium. The experimentally relevant macroscopic control variables are temperature, electrode potential, and the choice of the solvent and ions, and these need to be explicitly included in the computational model as well; this calls for a thermodynamic ensemble with fixed…
Explicit Solvation Matters: Performance of QM/MM Solvation Models in Nucleophilic Addition
2018
Nucleophilic addition onto a carbonyl moiety is strongly affected by solvent, and correctly simulating this solvent effect is often beyond the capability of single-scale quantum mechanical (QM) models. This work explores multiscale approaches for the description of the reversible and highly solvent-sensitive nucleophilic N|···C=O bond formation in an Me2N–(CH2)3–CH=O molecule. In the first stage of this work, we rigorously compare and test four recent quantum mechanical/molecular mechanical (QM/MM) explicit solvation models, employing a QM description of water molecules in spherical regions around both the oxygen and the nitrogen atom of the solute. The accuracy of the models is benchmarked…
Interaction of Charged Amino-Acid Side Chains with Ions: An Optimization Strategy for Classical Force Fields
2014
Many well-established classical biomolecular force fields, fitted on the solvation properties of single ions, do not necessarily describe all the details of ion pairing accurately, especially for complex polyatomic ions. Depending on the target application, it might not be sufficient to reproduce the thermodynamics of ion pairing, but it may also be necessary to correctly capture structural details, such as the coordination mode. In this work, we analyzed how classical force fields can be optimized to yield a realistic description of these different aspects of ion pairing. Given the prominent role of the interactions of negatively charged amino-acid side chains and divalent cations in many …
Cyclic tetraureas with variable flexibility--synthesis, crystal structures and properties.
2008
Macrocyclic molecules containing several amide or urea functions may serve as anion receptors. We describe the synthesis of 32-membered macrocycles, in which four rigid xanthene units (X) and/or diphenyl ether units (D) as flexible analogues are linked via urea groups. All six possible combinations of these units (XXXX, XXXD, XXDD, XDXD, XDDD and DDDD) were synthesized and two examples were characterised by single-crystal X-ray analyses (DDDD and two structures for XXXD). Both macrocycles showed distinct differences in their overall conformation and consequently in their hydrogen-bonding pattern. Hydrogen-bonded solvent molecules are found for both compounds and intramolecular hydrogen bond…
Protein dynamical transition vs. liquid-liquid phase transition in protein hydration water
2013
In this work, we compare experimental data on myoglobin hydrated powders from elastic neutron scattering, broadband dielectric spectroscopy, and differential scanning calorimetry. Our aim is to obtain new insights on the connection between the protein dynamical transition, a fundamental phenomenon observed in proteins whose physical origin is highly debated, and the liquid-liquid phase transition (LLPT) possibly occurring in protein hydration water and related to the existence of a low temperature critical point in supercooled water. Our results provide a consistent thermodynamic/dynamic description which gives experimental support to the LLPT hypothesis and further reveals how fundamental …
Relationship between Electron Affinity and Half-Wave Reduction Potential: A Theoretical Study on Cyclic Electron-Acceptor Compounds.
2016
A high-level ab initio protocol to compute accurate electron affinities and half-wave reduction potentials is presented and applied for a series of electron-acceptor compounds with potential interest in organic electronics and redox flow batteries. The comprehensive comparison between the theoretical and experimental electron affinities not only proves the reliability of the theoretical G3(MP2) approach employed but also calls into question certain experimental measurements, which need to be revised. By using the thermodynamic cycle for the one-electron attachment reaction A+e- →A- , theoretical estimates for the first half-wave reduction potential have been computed along the series of ele…
Fe(II) spin crossover complexes of a derivative of 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) functionalized with a carboxylic acid in the 3-pyridyl posit…
2019
Abstract The preparation of a new bis(pyrazol-1-yl)pyridine (1-bpp) derivative functionalized with a carboxylic acid in the 3-pyridyl position, bpp3-COOH ligand is reported together with the structure and spin-crossover (SCO) properties of [FeII(bpp3-COOH)2](ClO4)2·0.5EtOH·0.5H2O (1). Magnetic properties of 1 indicate that LS is favored. Desolvation leads to a gradual and incomplete SCO. Solvated and desolvated compounds show LIESST effect.
Behavior of Actinium, Alkaline, and Rare Earth Elements in Sr-Resin/Mineral Acid Systems
2015
In this work, the interactions between the divalent alkaline earth elements (AEE) (Sr, Ba, Ra), the trivalent rare earth elements (REE) (Ce-Lu, Y), and Ac(III) with Sr-resin were investigated in the presence of HNO3, HCl, HBr, HClO4, and HPF6. Distribution coefficients of these ions on the Sr-resin were determined under batch-loading conditions. Lastly, online column separations were performed to demonstrate the utility of these systems. Substantial differences in the behavior of the ions in solutions comprised of the five different acids were observed. These differences can partly be explained by a combination of ion exchange (primary) and extraction (solvation) mechanisms. From a practica…
Solid state solvation effect and reduced amplified spontaneous emission threshold value of glass forming DCM derivative in PMMA films
2015
Abstract Molecule crystallization is one of the limitations for obtaining high-gain organic laser systems. One of the examples is well known red laser dye 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). The lowest threshold value of amplified spontaneous emission was achieved by doping 2 wt% of DCM molecule in tris-(8-hydroxy quinoline) aluminum (Alq3) matrix. Further increase of the DCM dye concentration makes the system less efficient as its threshold value increases. It is due to large intermolecular interaction, which induces photoluminescence quenching. Compounds with reduced intermolecular interaction could be prospective in organic laser systems due to higher …