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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 8129-8138 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A nonlinear theory for the calculation of density and polarization of dipolar solvents near charged surfaces is developed by using a density functional approach. The theory is based on a weighted density approximation for the isotropic part of the density and the anisotropic (or dipolar) part is calculated by using a perturbative approach. The theory, however, retains the full nonlinear dependence on the surface charge density or the external field. Explicit numerical results are obtained for different values of the external field. It is found that the number density of the solvent near the surface increases with increasing surface charge density indicating the presence of electrostriction. The polarization is found to increase nonlinearly with the external field and exhibits the presence of dielectric saturation at high field strength. The predictions of the present nonlinear theory are compared with the results of Monte Carlo simulations and a good agreement is found for both the density and polarization near charged surfaces. The present simulations clearly reveal a nonlinear behavior of dipolar molecules in presence of the charged surfaces. Also, the nonlinear effects are found to be especially important for interfacial molecules, in agreement with the predictions of the analytical theory presented here. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 10439-10445 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dynamics of polarization relaxation at the solid–liquid interface is investigated theoretically by using time dependent density functional theory. The time dependence of the building up of solvent polarization next to a newly charged solid surface is calculated by solving both Markovian and non-Markovian equations of motion for density and momentum variables. The initial inhomogeneity of the medium is taken into account and it is calculated by using a weighted density functional theory. Explicit numerical results are obtained for the relaxation of solvent polarization at varying distances from the solid surface and the dynamics of interfacial relaxation is compared with that of the bulk. A slowing down of the rate of relaxation is found for interfacial molecules. However, the relaxation rate changes nonmonotonically with distance from the surface which can be attributed to the layering of solvent molecules in the interfacial region. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 8385-8391 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Computer simulation and theoretical results are given for the frequency dependent dielectric function of model electrolyte solutions. The influences of salt concentration, ionic charge, and solvent dipole moment are discussed. It is found that a substantial salt induced dielectric decrement persists up to the dispersion frequency. At higher frequencies, however, the dielectric constant of the solution is larger than that of the solvent giving a salt induced dielectric increment.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 4926-4931 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A self contained microscopic theory is described for ion solvation dynamics in dipolar fluids. The theory takes account of inertial and non-Markovian effects which are of critical importance for the fast initial phase of the relaxation of the ion–solvent energy. The theory also includes diffusional effects important at long times. The results obtained are shown to be in good agreement with recent computer simulation studies of ions in Stockmayer solvents.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 6531-6536 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the plausible mechanism of fast decomposition of acetyl chloride upon 1nπ* (CO) excitation through the selective C–Cl bond-fission on the lowest excited singlet state surface using ab initio quantum chemical methods. Effects of zero point energy corrections and of electron correlation have been considered. The pathway involves dissociation, via a φClφ*CO and a φClφ*C–Cl configurations where φ's stand for wave functions of σ-molecular orbitals.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 2083-2094 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The frequency dependent conductivity, σ(ω), of model electrolyte solutions is investigated employing molecular dynamics simulations. Approximate analytical theories are also derived and evaluated. It is found that σ(ω) is generally not a simple function and that its detailed frequency dependence contains much useful information about the structure and dynamics of ionic solutions. By varying molecular and state parameters such as the dipole moment and moment of inertia of the solvent, the ionic charge, the solution density, etc., we are able to obtain a physical interpretation of the behavior of σ(ω). For example, very interesting dynamical solvation effects as well as features associated with ion pairs are identified and described.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 2068-2073 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An approximate expression is derived for the dielectric function ε(k,ω). 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.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 4959-4966 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dielectric behavior of model electrolyte solutions is studied by molecular dynamics simulations. For the systems considered, it is found that the zero-frequency dielectric constant depends only on equilibrium properties and that there is no measurable "kinetic dielectric decrement.'' A theoretical explanation of the simulation results is presented. It is argued that no kinetic dielectric decrement exists for spherical ions in solvents of arbitrary molecular symmetry.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8367-8377 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Both the equilibrium and the dynamical aspects of solvation of a classical ion in a dense binary dipolar liquid are investigated by using a molecular theory. The theory properly includes the differing inter- and intramolecular correlations that are present in a binary mixture. As a result, the theory can explain several important aspects of the nonideality of equilibrium solvation energy (broadly known as preferential solvation) observed in experiments. We find that the nonideality of solvation depends strongly on both the molecular size and the magnitude of the dipole moment of the solvent molecules. The interactions among the solvent molecules play an important role in determining the extent of this nonideality. The dynamical calculations are based on a generalized Smoluchowski equation which has been used extensively for studies in one component liquid. For binary liquid, our study reveals rich and diverse behavior such as dependencies on the sizes, the transport coefficients and the polar properties of the components. The theory offers a detailed picture of the dependence of the solvation dynamics on the composition of the mixture. It is predicted that the dynamics of solvation in a binary liquid is, in general, nonexponential and that the details of the dynamics can be quite different from those in a one component liquid. In particular, the continuum model is found to be grossly inaccurate in describing the solvation dynamics in binary mixtures and rather extreme conditions are needed to recover the predictions of the continuum model which can be attributed to the nonideality of the solvation. The predicted results are used to study the dynamic solvent effects on the rate of an adiabatic electron transfer reaction in a binary liquid. The theoretical predictions are also compared with the available experimental results.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 6833-6839 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: It was recently proposed that collective polarization excitations, called dipolarons in analogy with the plasmons in the Coulomb systems, can exist for a long duration in a dense dipolar liquid. In this article, we present a microscopic analysis of the properties of such collective excitations, both at small and at intermediate wave vectors. The theory predicts the existence of dipolarons at values of the relevant parameters which are in good agreement with the computer simulation of Pollock and Alder. However, the predicted range of the parameter values in which the "true'' dipolaronic behavior is significant are rather too small to be important in common dipolar liquids like water, acetonitrile or methyl iodide. We find that the microscopic structure, especially the local orientational correlations and also the translational modes of the liquid, play important roles in determining the nature and the lifetime of the dipolaronic modes. Especially, these modes are more likely to occur at intermediate wave numbers if the translational contribution to the polarization relaxation is significant. The consequences of these theoretical predictions in experimental studies are discussed.
    Type of Medium: Electronic Resource
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