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We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics in numerous polar solvents, and ion solvation free energies in water--co-solvent mixtures. The first modification involves perturbing the macroscopic dielectric-flux interface condition at the solute--solvent interface with a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is a simple treatment of the microscopic interface potential (static potential). We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water--co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. The present work, together with previous studies of SLIC illustrating its accuracy for biomolecules in water, indicates it as a promising dielectric continuum model for accurate predictions of molecular solvation in a wide range of conditions.
Lithium based deep eutectic solvents (DESs) are excellent candidates for eco-friendly electrolytes in lithium ion batteries. While some of these DES have shown promising results, a clear mechanism of lithium ion transport in DESs is not yet establish
Recent studies on the solvation of atomistic and nanoscale solutes indicate that a strong coupling exists between the hydrophobic, dispersion, and electrostatic contributions to the solvation free energy, a facet not considered in current implicit so
In this work, a systematic protocol is proposed to automatically parametrize implicit solvent models with polar and nonpolar components. The proposed protocol utilizes the classical Poisson model or the Kohn-Sham density functional theory (KSDFT) bas
Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum
Continuum models to handle solvent and electrolyte effects in an effective way have a long tradition in quantum-chemistry simulations and are nowadays also being introduced in computational condensed-matter and materials simulations. A key ingredient