Mangesh I. Chaudhari

Utility of chemical computations in predicting solution free energies of metal ions

Abstract Here, we study quasi-chemical theory (QCT) for the free energies of divalent alkaline earth ions (Ba, Sr, Ca, Mg) in water, emphasizing that: (a) interactions between metal ions and proximal water molecules are as strong as traditional chemical effects; (b) QCT builds directly from accessible electronic structure calculations but rests on fully elaborated molecular statistical thermodynamics; (c) QCT offers choices of convenience in identifying coordination numbers for analysis. We investigate utilisation of direct QCT with inner-shell conditioning , alternative to the traditional conditioning motivated by a generalised van der Waals view. The alternative works well: deleterious non-Gaussian effects of van der Waals repulsive interactions are not serious, and the alternative conditioning improves the convenience of QCT calculations. Comparison between ab initio and force field molecular dynamics (AIMD and FFMD) with standard models suggests that FFMD likely exaggerates the anharmonicity in the thermal motion of inner-shell ion-water clusters. Together with the general encouraging support for the harmonic approximations implied by the conditioning, that observation helps explain the remarkable success of the cluster-based QCT solution free energies, which do not require assessment of all inner-shell occupancies by simulation.

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions

Progress in understanding liquid ethylene carbonate (EC) and propylene carbonate (PC) on the basis of molecular simulation, emphasizing simple models of interatomic forces, is reviewed. Results on the bulk liquids are examined from the perspective of anticipated applications to materials for electrical energy storage devices. Preliminary results on electrochemical double-layer capacitors based on carbon nanotube forests and on model solid-electrolyte interphase (SEI) layers of lithium ion batteries are considered as examples. The basic results discussed suggest that an empirically parameterized, non-polarizable force field can reproduce experimental structural, thermodynamic, and dielectric properties of EC and PC liquids with acceptable accuracy. More sophisticated force fields might include molecular polarizability and Buckingham-model description of inter-atomic overlap repulsions as extensions to Lennard-Jones models of van der Waals interactions. Simple approaches should be similarly successful also for applications to organic molecular ions in EC/PC solutions, but the important case of Li

Molecular Dynamics of Lithium Ion Transport in a Model Solid Electrolyte Interphase

^+

Strontium and barium in aqueous solution and a potassium channel binding site

+ deserves special attention because of the particularly strong interactions of that small ion with neighboring solvent molecules. To treat the Li

Nanoporous Hydrogels for the Observation of Anthrax Exotoxin Translocation Dynamics

^+

Density Functional Theory and Conductivity Studies of Boron-Based Anion Receptors

+ ions in liquid EC/PC solutions, we identify interaction models defined by empirically scaled partial charges for ion-solvent interactions. The empirical adjustments use more basic inputs, electronic structure calculations and ab initio molecular dynamics simulations, and also experimental results on Li