arXiv subjects

David M. Rogers

Publications and source records attributed to David M. Rogers.

21 records · Page 2Linked to original sources

arXiv2009

Quasi-Chemical and Structural Analysis of Polarizable Anion Hydration

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 experiment is obtained for whole salt hydration free energies using the polarizable AMOEBA force field. The quasi-chemical approach exactly partitions the solvation free energy into inner-shell, outer-shell packing, and outer-shell long-ranged contributions by means of a hard-sphere condition. Small conditioning radii, even well inside the first maximum of the ion-water(oxygen) radial distribution function, result in Gaussian behavior for the long-ranged contribution that dominates the ion hydration free energy. The spatial partitioning allows for a mean-field treatment of the long-ranged contribution, leading to a natural division into first-order electrostatic, induction, and van der Waals terms. The induction piece exhibits the strongest ion polarizability dependence, while the larger-magnitude first-order electrostatic piece yields an opposing but weaker polarizability dependence. In addition, a structural analysis is performed to examine the solvation anisotropy around the anions. As opposed to the hydration free energies, the solvation anisotropy depends more on ion polarizability than on ion size: increased polarizability leads to increased anisotropy. The water dipole moments near the ion are similar in magnitude to bulk water, while the ion dipole moments are found to be significantly larger than those observed in quantum mechanical studies. Possible impacts of the observed over-polarization of the ions on simulated anion surface segregation are discussed.

cond-mat.soft↗

arXiv2009

Polarization and Charge Transfer in the Hydration of Chloride Ions

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation, and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The Quantum Theory of Atoms in Molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared with the estimated quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2 level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

cond-mat.soft↗

arXiv2008

Modeling molecular and ionic absolute solvation free energies with quasi-chemical theory bounds

A recently developed statistical mechanical Quasi-Chemical Theory (QCT) has led to significant insights into solvation phenomena for both hydrophilic and hydrophobic solutes. The QCT exactly partitions solvation free energies into three components: 1) inner-shell chemical, 2) outer-shell packing, and 3) outer-shell long-ranged contributions. In this paper, we discuss efficient methods for computing each of the three parts of the free energy. A Bayesian estimation approach is developed to compute the inner-shell chemical and outer-shell packing contributions. We derive upper and lower bounds on the outer-shell long-ranged portion of the free energy by expressing this component in two equivalent ways. Local, high energy contacts between solute and solvent are eliminated by spatial conditioning in this free energy piece, leading to near-Gaussian distributions of solute-solvent interactions energies. Thus, the average of the two mean-field bounds yields an accurate and efficient free energy estimate. Aqueous solvation free energy results are presented for several solutes, including methane, perfluoromethane, water, and the sodium and chloride ions. The results demonstrate the accuracy and efficiency of the methods. The approach should prove useful in computing solvation free energies in inhomogeneous, restricted environments.

cond-mat.stat-mech↗