Related papers: Ion-water clusters, bulk medium effects, and ion h…
Experimental studies on ion-water clusters have provided insights into the microscopic aspects of hydration phenomena. One common view is that extending those experimental studies to larger cluster sizes would give the single ion absolute…
The interactions of hydrated ions with solution and interface partners are strong on a chemical energy scale. Here, we test the foremost \textit{ab initio theory} for evaluation of hydration free energies of ions, namely,…
Accurate predictions of the hydration free energy for anions typically have been more challenging than for cations. Hydrogen bond donation to the anion in hydrated clusters such as $\mathrm{F(H_2O)}_n{}^-$ can lead to delicate structures.…
Within the quasichemical approach, the hydration free energy of an ion is decomposed into a chemical term accounting for ion specific ion-water interactions within the coordination sphere and nonspecific contributions accounting for packing…
Ions transiting biomembranes might pass readily from water through ion-specific membrane proteins if those protein channels provide environments similar to the aqueous solution hydration environment. Indeed, bulk aqueous solution is an…
Anion hydration is complicated by H-bond donation between neighboring water molecules in addition to H-bond donation to the anion. This situation can lead to competing structures for chemically simple clusters like (H$_2$O)$_n$Cl$^-$ and to…
Chemical thermodynamic models of solvent and solute activities predict the equilibrium behaviour of aqueous solutions. How-ever, these models are semi-empirical. They represent micro-scale ion and solvent behaviours that control the…
A statistical thermodynamic development is given of a new implicit solvent model that avoids the traditional system size limitations of computer simulation of macromolecular solutions with periodic boundary conditions. This implicit solvent…
The association of ions in electrolyte solutions at very low concentration and low temperature is studied using computer simulations and quasi-chemical ion-pairing theory. The specific case of the restricted primitive model (charged hard…
The propensity for ion-pairing can often dictate the thermodynamic and kinetic properties of electrolyte solutions. Fast and accurate estimates of ion-pairing can thus be extremely valuable for supplementing design and screening efforts for…
A well known, if little documented, problem in many molecular simulations of aqueous ionic solutions at finite concentrations is that unrealistic cation-cation associations are frequently found. One might suspect a defect in the ion-ion…
Quasi-chemical theory is utilized to analyze the roles of solute polarization and size in determining the structure and thermodynamics of bulk anion hydration for the Hofmeister series Cl$^-$, Br$^-$, and I$^-$. Excellent agreement with…
Molecular dynamics simulations of aqueous NaCl, KCl, NaI, and KI solutions are used to study the effects of salts on the properties of the liquid/vapor interface. The simulations use the models which include both charge transfer and…
The quasi-chemical organization of the potential distribution theorem -- molecular quasi-chemical theory (QCT) -- enables practical calculations and also provides a conceptual framework for molecular hydration phenomena. QCT can be viewed…
Several thermodynamic properties of ice Ih, II, and III are studied by a quasi-harmonic approximation and compared to results of quantum path integral and classical simulations. This approximation allows to obtain thermodynamic information…
Ion dehydration has been hypothesized to strongly influence separation performance in membrane systems and ion transport in nanoscale channels. However, the molecular details of ion dehydration in membranes are not well understood, in…
We investigate the behavior of hydrated sulfonated polysulfones over a range of ion contents through differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and molecular dynamics (MD) simulations.…
Effects of presence of ions, at moderate to high concentrations, on dynamical properties of water molecules are investigated through classical molecular dynamics simulations using two well known non-polarizable water models. Simulations…
The hydration of ions in nanoscale hydrated clusters is ubiquitous and essential in many physical and chemical processes. Here we show that the hydrolysis reaction is strongly affected by relative humidity. The hydrolysis of CO32- with n =…
Quantitative prediction of thermodynamic properties in solution is essential for translating atomistic simulations into reliable chemical insight. As an exemplar system, the behaviour of CaCO$_3$ in water has been widely studied to…