@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 {2982,
title = {SOLVATION DYNAMICS IN ELECTROLYTE-SOLUTIONS},
journal = {Journal of Chemical Physics},
volume = {100},
number = {2},
year = {1994},
note = {ISI Document Delivery No.: MT007Times Cited: 33Cited Reference Count: 40},
month = {Jan},
pages = {1552-1558},
type = {Article},
abstract = {A microscopic theory of the dynamics of ion solvation in electrolyte solutions is given. Consistent with the pure solvent case, the theory predicts a very fast and important inertial relaxation at short times. This is followed by oscillations and an extremely slow long-time decay associated with the formation of an equilibrium {\textquoteright}{\textquoteright}ion atmosphere{\textquoteright}{\textquoteright} about the newly charged particle.},
keywords = {DIELECTRIC-RELAXATION, INVARIANT EXPANSION, ION, LIQUIDS, MEAN SPHERICAL MODEL, ORNSTEIN-ZERNIKE EQUATION, SIMULATIONS, SOLVENT, SPHERES},
isbn = {0021-9606},
url = {://A1994MT00700085},
author = {Chandra, A. and Patey, G. N.}
}
@article {2748,
title = {DIELECTRIC-RELAXATION OF DIPOLAR LIQUIDS},
journal = {Journal of Chemical Physics},
volume = {99},
number = {3},
year = {1993},
note = {ISI Document Delivery No.: LN782Times Cited: 19Cited Reference Count: 33},
month = {Aug},
pages = {2068-2073},
type = {Article},
abstract = {An approximate expression is derived for the dielectric function epsilon(k, omega). The theory includes inertial and non-Markovian effects and is free of adjustable parameters. For the k = 0 case, detailed comparisons are made with computer simulation results for dipolar soft-sphere and Stockmayer fluids, and the theory is shown to be qualitatively sound at both low and high frequencies. The present approximation should be very useful in developing a theory of solvation dynamics which properly includes important inertial effects.},
keywords = {COMPUTER-SIMULATION, electrostatic, equation, INVARIANT EXPANSION, ION SOLVATION, LIQUIDS, MEAN SPHERICAL MODEL, MOLECULAR LIQUIDS, ORNSTEIN-ZERNIKE, PERIODIC BOUNDARY-CONDITIONS, POLAR, SOLVATION DYNAMICS, SYSTEMS},
isbn = {0021-9606},
url = {://A1993LN78200067},
author = {Chandra, A. and Wei, D. Q. and Patey, G. N.}
}
@article {2930,
title = {ORIENTATIONAL ORDER IN SIMPLE DIPOLAR FLUIDS - DENSITY-FUNCTIONAL THEORY AND ABSOLUTE-STABILITY CONDITIONS},
journal = {Physical Review E},
volume = {47},
number = {1},
year = {1993},
note = {ISI Document Delivery No.: KY134Times Cited: 59Cited Reference Count: 29},
month = {Jan},
pages = {506-512},
type = {Article},
abstract = {The formation of ferroelectric liquid crystals by simple dipolar models is investigated using density-functional theory and absolute-stability analysis. It is emphasized that for such systems well defined results can only be found by specifying exactly how the long-range dipolar interactions are treated. Explicit formal expressions are derived for mean-reaction-field boundary conditions and these are combined with integral-equation approximations in order to obtain numerical results for fluids of dipolar hard and soft spheres. The calculations predict isotropic-to-ferroelectric-nematic transitions in qualitative agreement with computer simulations. The quantitative agreement, however, is rather poor.},
keywords = {COMPUTER-SIMULATION, ELECTROSTATIC SYSTEMS, equation, HARD-SPHERES, INVARIANT EXPANSION, MEAN SPHERICAL MODEL, ORNSTEIN-ZERNIKE, PERIODIC BOUNDARY-CONDITIONS, POLAR SYSTEMS, TRANSITION},
isbn = {1063-651X},
url = {://A1993KY13400062},
author = {Wei, D. Q. and Patey, G. N. and Perera, A.}
}
@article {7179,
title = {A MEAN FIELD-THEORY FOR FLUIDS OF MULTIPOLAR PARTICLES IN CONTACT WITH A POLARIZABLE WALL},
journal = {Journal of Chemical Physics},
volume = {97},
number = {6},
year = {1992},
note = {ISI Document Delivery No.: JN146Times Cited: 15Cited Reference Count: 27},
month = {Sep},
pages = {4372-4379},
type = {Article},
abstract = {Fluids of multipolar particles in contact with a semi-infinite polarizable hard wall are considered. A mean field theory which reduces the many-body electrostatic wall-solvent interactions to an effective pair potential is described. The effective potential can be employed in conjunction with the reference hypernetted-chain approximation, or some other integral equation theory, to obtain a self-consistent solution for the wall-solvent correlation function and hence the solvent structure at the interface. Explicit results are given for dipolar hard sphere fluids in contact with walls having dielectric constants ranging from 1 to infinity. For this system, it is shown that contributions to the wall-solvent potential from images of other particles are very important and act strongly against the direct "self-image" interaction.},
keywords = {ASYMPTOTIC-BEHAVIOR, CHARGED SURFACES, DIPOLAR HARD-SPHERES, INVARIANT EXPANSION, LIQUID WATER, MOLECULAR-DYNAMICS, NONSPHERICAL PARTICLES, ORNSTEIN-ZERNIKE EQUATION, SPHERICAL MODEL, WATER-LIKE PARTICLES},
isbn = {0021-9606},
url = {://A1992JN14600051},
author = {Berard, D. R. and Patey, G. N.}
}
@article {6968,
title = {THE APPLICATION OF INTEGRAL-EQUATION THEORIES TO FLUIDS OF NONSPHERICAL PARTICLES NEAR A UNIFORM PLANAR WALL},
journal = {Journal of Chemical Physics},
volume = {95},
number = {7},
year = {1991},
note = {ISI Document Delivery No.: GH356Times Cited: 37Cited Reference Count: 39},
month = {Oct},
pages = {5281-5288},
type = {Article},
abstract = {A general reduction of the Ornstein-Zernike equation is given for molecular fluids near a planar wall. This allows integral equation approximations such as the hypernetted-chain or reference hypernetted-chain (RHNC) theories to be solved numerically for such systems. Dipolar hard sphere fluids near a hard wall are considered in detail and RHNC solutions are obtained. The results are compared with previous calculations for curved surfaces. The RHNC result for the asymptotic behavior of the wall-solvent pair correlation function at large separations is derived and compared with expressions given by classical continuum theory and by exact analysis.},
keywords = {AQUEOUS-ELECTROLYTE SOLUTIONS, DIPOLAR HARD-SPHERES, ELECTRICAL DOUBLE-LAYER, HYPERNETTED-CHAIN, INFINITE DILUTION, INVARIANT EXPANSION, MEAN, MOLECULAR-SOLVENT MODEL, ORIENTATIONAL, ORNSTEIN-ZERNIKE EQUATION, SPHERICAL MODEL, STRUCTURE},
isbn = {0021-9606},
url = {://A1991GH35600061},
author = {Berard, D. R. and Patey, G. N.}
}
@article {7130,
title = {THE CRYSTALLIZATION OF ALKALI-HALIDES FROM AQUEOUS-SOLUTION - AN APPLICATION OF DENSITY-FUNCTIONAL THEORY},
journal = {Journal of Chemical Physics},
volume = {95},
number = {1},
year = {1991},
note = {ISI Document Delivery No.: FT847Times Cited: 3Cited Reference Count: 23},
month = {Jul},
pages = {485-493},
type = {Article},
abstract = {Density-functional theory is applied to the problem of salt crystallization from solution and explicit results are given for model aqueous alkali-halide systems. Both direct- and Fourier-space methods of calculation are considered and it is found that only the direct (i.e., r space) method converges sufficiently rapidly to provide reliable results for ionic crystals at 25-degrees-C. It is shown that the density-functional method is capable of predicting crystallization, but that the solid-state parameters and, for some salts, the crystal structures obtained are in poor agreement with experiment or computer simulations. The calculated crystal/solution coexistence concentrations are found to be extremely sensitive to the short-range part of the interionic pair potentials. This is consistent with earlier observations that the activity coefficients of model aqueous alkali-halide solutions are very strongly dependent upon the short-range ion-ion interactions. Therefore, we do not believe that this sensitivity to details of the short-range interionic potentials is an artifact of theoretical approximations, but rather a real effect significantly influencing crystallization.},
keywords = {APPROXIMATION, INVARIANT EXPANSION, MEAN SPHERICAL MODEL, ORNSTEIN-ZERNIKE EQUATION, SIMULATION, SPHERES, TRANSITION, WATER},
isbn = {0021-9606},
url = {://A1991FT84700048},
author = {Ursenbach, C. P. and Patey, G. N.}
}
@article {7146,
title = {DIELECTRIC-RELAXATION OF ELECTROLYTE-SOLUTIONS},
journal = {Journal of Chemical Physics},
volume = {94},
number = {10},
year = {1991},
note = {ISI Document Delivery No.: FL001Times Cited: 29Cited Reference Count: 49},
month = {May},
pages = {6795-6806},
type = {Article},
abstract = {The dielectric relaxation theory of electrolyte solutions is formulated in terms of solvent-solvent, ion-ion, and ion-solvent van Hove time correlation functions. General wave vector frequency-dependent expressions are given for the longitudinal components of the relevant (i.e., polarization-polarization, current-current, current-polarization, polarization-current) time correlation functions and of the susceptibility, dielectric, and conductivity tensors. The Kerr theory relating the distinct and self parts of the van Hove functions is extended to mixtures of molecular fluids and solved explicitly in the k {\textendash}> 0 limit for solutions of spherical ions (assuming that the self part of the van Hove functions is given by Fick{\textquoteright}s law) immersed in polar solvents. At this level of theory, the van Hove functions, the time correlation functions and the susceptibilities are all found to depend upon coupled ion-solvent motion. However, the dynamical coupling terms are shown to cancel exactly in the final expressions for the conductivity and dielectric constant yielding relatively simple results. Specifically, the conductivity obtained is independent of frequency and is related to the self diffusion constants of the ions by the Nernst-Einstein expression. If a spherical diffusor model is chosen for the solvent, then the frequency-dependent dielectric constant is given by a Debye-type formula with a concentration dependent relationship connecting the Debye and self reorientational relaxation times of the solvent. These results are discussed in the context of previous theories and experimental observations. It is shown that, although obviously oversimplified, the present theory does qualitatively predict the correct concentration dependence of the observed relaxation times for a number of salt solutions.},
keywords = {DIPOLAR LIQUIDS, DISPERSION, FLUIDS, friction, INVARIANT EXPANSION, LIQUIDS, MEAN SPHERICAL MODEL, MOLECULAR THEORY, ORNSTEIN-ZERNIKE EQUATION, POLAR, TRANSLATIONAL DIFFUSION},
isbn = {0021-9606},
url = {://A1991FL00100048},
author = {Wei, D. Q. 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.}
}
@article {6958,
title = {INTERACTION FREE-ENERGY BETWEEN PLANAR WALLS IN DENSE FLUIDS - AN ORNSTEIN-ZERNIKE APPROACH WITH RESULTS FOR HARD-SPHERE, LENNARD-JONES, AND DIPOLAR SYSTEMS},
journal = {Physical Review A},
volume = {44},
number = {12},
year = {1991},
note = {ISI Document Delivery No.: GW604Times Cited: 63Cited Reference Count: 43},
month = {Dec},
pages = {8224-8234},
type = {Article},
abstract = {The interaction free energy per unit area between planar walls is given as a convolution of wall-solvent pair-correlation functions. This result, derived from the large radius limit of the macrosphere-solvent Ornstein-Zernike equations, and from the hypernetted-chain closure, provides a statistical-mechanical basis for the Derjaguin approximation, and is both generally applicable and computationally tractable. It is found that the interaction between hard walls in a hard-sphere fluid is oscillatory, and in good agreement with simulations. The van der Waals attraction emerges from asymptotic analyses of Lennard-Jones and dipolar fluids, and the full expression allows calculation of this quantity down to molecular separations. This is demonstrated by numerical results for dipolar fluids.},
keywords = {APPROXIMATION, ELECTRICAL DOUBLE-LAYERS, ELECTROLYTES, equation, HYPERNETTED-CHAIN, INHOMOGENEOUS FLUIDS, INVARIANT EXPANSION, MODEL, MONTE-CARLO, SURFACES},
isbn = {1050-2947},
url = {://A1991GW60400049},
author = {Attard, P. and Berard, D. R. and Ursenbach, C. P. and Patey, G. N.}
}