@article {4662,
title = {Phase behavior of ionic solutions: Comparison of the primitive and explicit solvent models},
journal = {Journal of Chemical Physics},
volume = {110},
number = {3},
year = {1999},
note = {ISI Document Delivery No.: 156YMTimes Cited: 20Cited Reference Count: 39},
month = {Jan},
pages = {1633-1637},
type = {Article},
abstract = {Grand canonical Monte Carlo calculations are used to investigate the demixing transition in model ionic solutions where the solvent is explicitly included. Charged hard sphere ions in hard sphere, dipolar hard sphere and quadrupolar hard sphere solvents are considered and the results are compared with the primitive (continuum solvent) model. For all solvents considered, it is found that the demixing transition is in the same general region of the phase diagram and is roughly described by liquid-vapor equilibrium in the primitive model. However, details such as the precise location of the critical point and the width of the unstable region depend upon the exact nature of the solvent. (C) 1999 American Institute of Physics. [S0021-9606(99)50203-1].},
keywords = {BINARY, CHARGED HARD-SPHERES, CONSOLUTE POINT, CRITICAL EXPONENT, ELECTROLYTE-SOLUTIONS, EQUILIBRIA, FLUIDS, FREE-ENERGY, LIQUID-VAPOR COEXISTENCE, MIXTURE, MONTE-CARLO},
isbn = {0021-9606},
url = {://000078030500034},
author = {Shelley, J. C. and Patey, G. N.}
}
@article {4442,
title = {An investigation of dynamical density functional theory for solvation in simple mixtures},
journal = {Journal of Chemical Physics},
volume = {108},
number = {15},
year = {1998},
note = {ISI Document Delivery No.: ZH114Times Cited: 27Cited Reference Count: 48},
month = {Apr},
pages = {6378-6386},
type = {Article},
abstract = {Linear and nonlinear versions of time dependent density functional theory are solved for a single solute particle in a simple binary solvent. All particles interact with Lennard-Jones potentials. The theoretical results are compared with molecular dynamics calculations. It is shown that the nonlinear theory is necessary in order to obtain a good quantitative description of selective solvation dynamics. The linear theory is only of qualitative value. Also, attention is drawn to a previously little appreciated problem which arises when one attempts to compare time dependent density functional theory with computer simulation or experimental results. The difficulty involves matching the theoretical and absolute time scales and is discussed in detail in this paper. (C) 1998 American Institute of Physics. [S0021-9606(98)50615-0].},
keywords = {BINARY DIPOLAR LIQUIDS, COLLECTIVE ORIENTATIONAL RELAXATION, density, DIELECTRIC-RELAXATION, ELECTROLYTE-SOLUTIONS, ION SOLVATION, MOLECULAR THEORY, NONPOLAR SOLVATION, NUMBER, POLAR, SURROGATE HAMILTONIAN DESCRIPTION},
isbn = {0021-9606},
url = {://000073073700034},
author = {Yoshimori, A. and Day, T. J. F. and Patey, G. N.}
}
@article {4441,
title = {Theory of ion solvation dynamics in mixed dipolar solvents},
journal = {Journal of Chemical Physics},
volume = {109},
number = {8},
year = {1998},
note = {ISI Document Delivery No.: 114ZNTimes Cited: 38Cited Reference Count: 32},
month = {Aug},
pages = {3222-3231},
type = {Article},
abstract = {Time dependent density functional theory in its "extended linear" or "surrogate" form is used to investigate the dynamics of selective ion solvation in binary dipolar solvents. It is shown that simple analytical approximations that trap the basic physics of the solvation process can be obtained. In particular, it is found that the relaxation of:the solvent number densities about a charged solute is governed by two distinct modes clearly associated with electrostriction and redistribution processes. This is consistent with the physical picture suggested by molecular dynamics (MD) simulations. The solvent polarization relaxation is also dominated by two modes associated with the-two rotational diffusion constants of the binary solvent. In addition to the analytical approximations, full numerical solutions of the extended linear theory are obtained and the dependence of the relaxation on solvent density and solute charge is discussed. Detailed comparisons of the theory with MD simulations for a closely related model indicate that the theory is qualitatively correct, but quantitatively poor generally predicting relaxation rates which are too fast. This is due mainly to the neglect of inertial or non-Markovian effects in the theoretical approach. (C) 1998 American Institute of Physics. [S0021-9606(98)50132-8]},
keywords = {COLLECTIVE ORIENTATIONAL RELAXATION, DIELECTRIC-RELAXATION, ELECTROLYTE-SOLUTIONS, HARD-SPHERES, INVARIANT EXPANSION, LIQUIDS, MEAN, MIXTURES, MOLECULAR THEORY, ORNSTEIN-ZERNIKE EQUATION, SPHERICAL MODEL},
isbn = {0021-9606},
url = {://000075639200032},
author = {Yoshimori, A. and Day, T. J. F. and Patey, G. N.}
}
@article {3924,
title = {An investigation of the influence of solute size and insertion conditions on solvation thermodynamics},
journal = {Journal of Chemical Physics},
volume = {106},
number = {19},
year = {1997},
note = {ISI Document Delivery No.: WZ032Times Cited: 32Cited Reference Count: 52},
month = {May},
pages = {8165-8195},
type = {Article},
abstract = {In this paper we examine the influence of solute size and insertion conditions on solvent structural changes and excess thermodynamic properties in the infinite dilution limit. A general integral equation approach which can be applied under arbitrary conditions is given and isothermal-isochoric and isothermal-isobaric insertions are discussed in detail. Scaling relationships valid in the large solute limit are determined for both structural and thermodynamic properties. This is done by considering macroscopic thermodynamic relationships and explicit evaluation of low solvent density expansions of pair correlation functions. The hypernetted-chain and reference hypernetted-chain closure approximations are used to obtain numerical results for the insertion of hard sphere solutes of varying diameter into hard sphere, dipolar hard sphere and water-like solvents. The results obtained give a good deal of insight into the nature of solvation of inert solutes. It is shown that for all three solvents the excess properties are very well represented by a function obtained by summing terms proportional to the solute volume, surface area and diameter. One would expect such a result for large solutes, but here we show that this expression extrapolates all the way down to solutes comparable in size to the solvent particles. Further, it is shown that both the numerical value, and, more importantly, the physical interpretation of the excess thermodynamic properties strongly depend on the insertion conditions. Under all insertion conditions the chemical potential is a local property in the sense that it is completely determined by solute-solvent correlations which are important only in the immediate vicinity of the solute. However, this is not true of the excess energy, enthalpy and entropy which all contain nonlocal contributions arising essentially from changes in the actual or effective solvent density depending on the insertion conditions. We demonstrate that the nonlocal contributions can be very significant and therefore the excess energies, enthalpies and entropies often cannot provide useful information about solvent structure near solutes. This has significant implications for models which attempt to rationalize excess thermodynamics in terms of local solvent structure in the vicinity of solute particles. (C) 1997 American Institute of Physics.},
keywords = {COMPUTER-SIMULATION, ELECTROLYTE-SOLUTIONS, FREE-ENERGIES, HARD-SPHERES, HYDROPHOBIC HYDRATION, HYPERNETTED-CHAIN APPROXIMATION, INVARIANT EXPANSION, MEAN, ORNSTEIN-ZERNIKE EQUATION, SPHERICAL MODEL, TEMPERATURE-DEPENDENCE},
isbn = {0021-9606},
url = {://A1997WZ03200027},
author = {Cann, N. M. and Patey, G. N.}
}
@article {3184,
title = {STABILITY OF BINARY-MIXTURES - SUPERSATURATION LIMITS OF AQUEOUS ALKALI-HALIDE SOLUTIONS},
journal = {Journal of Chemical Physics},
volume = {100},
number = {5},
year = {1994},
note = {ISI Document Delivery No.: MY349Times Cited: 20Cited Reference Count: 38},
month = {Mar},
pages = {3827-3842},
type = {Article},
abstract = {The stability of ionic binary mixtures is investigated by an integral equation method. In presenting the theory a distinction is made between primary and secondary stability criteria, and this distinction is used to clarify some misconceptions in the literature. The derived stability criteria are then applied to electrolyte solutions as well as to a simple binary mixture. In a simple mixture of hard spheres in wafer, both mechanical and material instabilities are found near the spinodal line along with evidence of long-range hydrophobic forces. Results for the electrolyte solutions indicate that salts with only large ions, such as CsI, and those with a smaller ion, such as Na+ or K+, behave differently near the spinodal line. CsI acts hydrophobicly, and appears to undergo demixing from the solvent, whereas NaCl and KCl, which bind the solvent more tightly, do not show clear signs of any such demixing, but do appear to become mechanically unstable. Finally, some recent results of Chen and Forstmann [J. Chem; Phys. 97, 3696 (1992)] are discussed and applied to the present systems.},
keywords = {DIPOLAR, ELECTROLYTE-SOLUTIONS, equation, FLUID MIXTURES, HYPERNETTED-CHAIN APPROXIMATION, INSTABILITY, NEUTRAL HARD-SPHERES, PHASE, SEPARATION, SPINODAL CURVE},
isbn = {0021-9606},
url = {://A1994MY34900047},
author = {Ursenbach, C. P. and Patey, G. N.}
}
@article {6959,
title = {CONTINUUM ELECTROSTATIC INTERACTIONS BETWEEN PLANAR LATTICES OF DIPOLES AND THE POSSIBLE RELEVANCE TO THE HYDRATION FORCE},
journal = {Physical Review A},
volume = {43},
number = {6},
year = {1991},
note = {ISI Document Delivery No.: FD045Times Cited: 11Cited Reference Count: 37},
month = {Mar},
pages = {2953-2962},
type = {Article},
abstract = {The electrostatic interaction between two planar dipolar lattices in dielectric continua is investigated. If there are no dielectric images, the pressure is equally likely to be attractive or repulsive, depending upon the relative lateral displacement of the two lattices. In addition to perfect dipolar lattices, we consider the effects of real dipoles, of disorder, and of finite-sized domains. When the surfaces constitute the boundary between dielectric media, and when there are no correlations between the two surfaces, then there occurs a strong exponentially decaying repulsion due to the interaction between a lattice and its dielectric images. The relevance of this repulsion to the hydration force is discussed, and an experimental test that should discriminate between different theories for that force is proposed.},
keywords = {BILAYER SYSTEMS, DEPENDENCE, DOUBLE-LAYER, ELECTROLYTE-SOLUTIONS, MICA, MOBILE, MODEL, ORIENTABLE DIPOLES, polarization, SURFACES, WATER},
isbn = {1050-2947},
url = {://A1991FD04500037},
author = {Attard, P. and Patey, G. N.}
}
@article {7145,
title = {DIELECTRIC-RELAXATION OF LIQUID-MIXTURES},
journal = {Journal of Chemical Physics},
volume = {94},
number = {10},
year = {1991},
note = {ISI Document Delivery No.: FL001Times Cited: 15Cited Reference Count: 41},
month = {May},
pages = {6785-6794},
type = {Article},
abstract = {General expressions in terms of van Hove time correlation functions are given for the wave vector frequency-dependent dielectric function of multicomponent mixtures. The van Hove functions are obtained by applying the Kerr approximation and the dielectric relaxation at zero wave vector is considered in detail. At this level of theory, the frequency-dependent dielectric constant depends upon the self-reorientational correlation times of the various species involved and upon the equilibrium pair correlation functions. It is shown that if the self-correlation times are assumed to be given by the Stokes-Debye relationship, and if the equilibrium direct correlation functions obey certain relatively weak conditions, then for particles of equal size (i.e., the self-correlation times are the same for all species) the dielectric relaxation behavior can be described by a simple Debye formula with a single concentration-dependent relaxation time. This observation is independent of the number of components, of the concentration, and of the molecular dipole moments of the different species present. It may help explain why for some binary mixtures of polar molecules experimental measurements indicate only a single relaxation channel. The exact Kerr result for binary mixtures is expressed explicitly as the sum of two Lorentzians, and some numerical results are given for solutions of dipolar hard spheres of different diameter.},
keywords = {CONSTANT, DIPOLAR LIQUIDS, DYNAMICS, ELECTROLYTE-SOLUTIONS, INVARIANT EXPANSION, MEAN SPHERICAL MODEL, MOLECULAR LIQUIDS, ORNSTEIN-ZERNIKE EQUATION, SOLVATION, TRANSLATIONAL DIFFUSION},
isbn = {0021-9606},
url = {://A1991FL00100047},
author = {Wei, D. Q. and Patey, G. N.}
}