arXiv subjects

Lawrence R. Pratt

Publications and source records attributed to Lawrence R. Pratt.

40 records · Page 3Linked to original sources

arXiv1994

Theoretical calculation of the water ion product K_W

A dielectric solvation model is applied to the prediction of the equilibrium ionization of liquid water over a wide range of density and temperature with the objective of calibrating that model for the study of ionization in water of organic acids, {\it e.g.\/}, proteins and nucleic acids. The model includes an approximate description of the polarizability of the dissociating water molecule. The calculated pK$_W$ are very sensitive to the value of the radii that parameterize the model. The radii required for the spherical molecular volumes of the water molecule in order to fit the experimental ion product are presented and discussed. These radii are larger than those commonly used. They decrease with increasing density as would be guessed but the rate of decrease is slight. They increase with increasing temperature, a variation opposite to what would be guessed if radii were strictly viewed as a distance of closest approach. The molecular theoretical principles that might provide an explanation of the thermodynamic state dependence of these radii are discussed.

chem-ph↗

arXiv1994

Comparison of electron density functional models

Presented here are calculations of the distortion of the density of an electron gas due to the electrostatic field of a proton. Several models based upon the local density approximation (LDA) of density functional theory [linear response theory, Kohn-Sham (KS), optimized Thomas-Fermi theory (OTF), and OTF plus perturbation corrections] are compared with one another. These models, in turn, are compared with available results of quantum Monte Carlo (QMC) calculations for the same system. Comparison of the KS results with the OTF results shows a very reasonable agreement that seems to be progressively improvable. This provides encouragement for the application of the OTF model to condensed phase systems. The QMC calculations of the density do not agree well with the density functional results. The reasons for this poor agreement are not clear. This particular system is expected to be an ideal one for application of the LDA and, thus, the poor agreement is of fundamental importance. The lack of detail presented in the available QMC results leads us to conclude that the QMC calculations should be attempted again. in print: Molec. Phys. 82, 245-261(1994)

chem-ph↗

arXiv1994

Ion Pair Potentials-of-Mean-Force in Water

Recent molecular simulation and integral equation results alkali-halide ion pair potentials-of-mean-force in water are discussed. Dielectric model calculations are implemented to check that these models produce that characteristic structure of contact and solvent-separated minima for oppositely charged ions in water under physiological thermodynamic conditions. Comparison of the dielectric model results with the most current molecular level information indicates that the dielectric model does not, however, provide an accurate description of these potentials-of-mean-force. We note that linear dielectric models correspond to modelistic implementations of second-order thermodynamic perturbation theory for the excess chemical potential of a distinguished solute molecule. Therefore, the molecular theory corresponding to the dielectric models is second-order thermodynamic perturbation theory for that excess chemical potential. The second-order, or fluctuation, term raises a technical computational issue of treatment of long-ranged interactions similar to the one which arises in calculation of the dielectric constant of the solvent. It is contended that the most important step for further development of dielectric models would be a separate assessment of the first-order perturbative term (equivalently the {\it potential at zero charge} ) which vanishes in the dielectric models but is generally nonzero. Parameterization of radii and molecular volumes should then be based of the second-order perturbative term alone. Illustrative initial calculations are presented and discussed.

chem-ph↗

arXiv1994

Tests of Dielectric Model Descriptions of Chemical Charge Displacements in Water

A dielectric model of electrostatic solvation is applied to describe potentials of mean force in water along reaction paths for: a) formation of a sodium chloride ion pair; b) the symmetric SN2 exchange of chloride in methylchloride; and c) nucleophilic attack of formaldehyde by hydroxide anion. For these cases simulation and XRISM results are available for comparison. The accuracy of model predictions varies from spectacular to mediocre. It is argued that: a) dielectric models are physical models, even though simplistic and empirical; b) their successes suggest that second-order perturbation theory is a physically sound description of free energies of electrostatic solvation; and c) the most serious deficiency of the dielectric models lies in the definition of cavity volumes. Second-order perturbation theory should therefore be used to refine the dielectric models. These dielectric models make no attempt to assess the role of packing effects but for solvation of classical electrostatic interactions the dielectric models sometimes perform as well as the more detailed XRISM theory.

chem-ph↗