Cooperative Molecular Behavior and Field Effects on Liquids: Experimental Considerations

Evans, Gareth J.

doi:10.1002/9780470142875.ch4

Cited by 5 publications

(1 citation statement)

References 82 publications

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“…56 This is the special case of the RSE function, with ␤ = 1. Dielectric spectroscopy experimental data for small polar molecule liquids 7,38,42,[57][58][59][60] suggest that this ratio of times is typically between 0.01 and 0.2. For Eq.…”

Section: G͑0͒mentioning

confidence: 99%

Rounded stretched exponential for time relaxation functions

Powles

Heyes

Rickayzen

et al. 2009

The Journal of Chemical Physics

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A rounded stretched exponential function is introduced, C(t)=exp{(tau(0)/tau(E))(beta)[1-(1+(t/tau(0))(2))(beta/2)]}, where t is time, and tau(0) and tau(E) are two relaxation times. This expression can be used to represent the relaxation function of many real dynamical processes, as at long times, t>>tau(0), the function converges to a stretched exponential with normalizing relaxation time, tau(E), yet its expansion is even or symmetric in time, which is a statistical mechanical requirement. This expression fits well the shear stress relaxation function for model soft soft-sphere fluids near coexistence, with tau(E)<

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Section: G͑0͒mentioning

confidence: 99%

Rounded stretched exponential for time relaxation functions

Powles

Heyes

Rickayzen

et al. 2009

The Journal of Chemical Physics

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Ionic Mobilities at Infinite Dilution: Structural Aspects

Kessler

Kumeev

Vaisman

et al. 1989

Ber Bunsenges Phys Chem

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Empirical correlations between ionic mobilities and parameters characteristic of the solvent molecules motions for a variety of single ions and 1‐1 electrolytes at infinite dilution in 19 one‐component solvents and 8 aqueous‐nonaqueous mixed solvents are found, presented and discussed. The parameters are the self‐diffusion coefficient, the dipole relaxation time, the rotational correlation time of various NMR vectors, and the residence time of solvent molecules in the first ion solvation shell. The residual friction coefficients are considered in a more theoretical vein.

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Calculation of the Microscopic and Macroscopic Linear and Nonlinear Optical Properties of Acetonitrile: I. Accurate Molecular Properties in the Gas Phase and Susceptibilities of the Liquid in Onsager's Reaction-Field Model

2003

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As part of a program to investigate the linear and nonlinear susceptibilities of acetonitrile in the condensed phase, we report on the accurate calculation of the molecular electric properties of acetonitrile, taking into account geometry and basis set effects, static and dynamic electronic correlation, vibrational contributions, and frequency dispersion. All correlated single reference state methods as well as the multireference SCF with a Møller−Plesset second-order perturbation correction (MRMP2) yield similar values for the electronic contribution to the polarizability α and the second hyperpolarizability γ. For the first hyperpolarizability, however, differences between the highly correlated methods CCSD(T) and MRMP2 remain. Vibrational contributions to the electric properties are calculated analytically and using two numerical finite difference methods at the Hartree−Fock level and at the correlated second-order Møller−Plesset level using finite field difference methods. Basis set convergence and convergence with the level of anharmonicity are examined. Computed values of the quantity μβ∥(−2ω; ω, ω)/(3kT) + γav(−2ω; ω, ω, 0) agree with temperature-dependent experimental values at two different frequencies within 10%. Using the highest correlated methods, liquid-phase susceptibilities are computed in the dipolar Onsager reaction-field approximation. Excellent agreement with experiment for the relative permittivity and the refractive indices is found as well as acceptable agreement for the nonlinear susceptibility.

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Cooperative Molecular Behavior and Field Effects on Liquids: Experimental Considerations

Cited by 5 publications

References 82 publications

Rounded stretched exponential for time relaxation functions

Rounded stretched exponential for time relaxation functions

Ionic Mobilities at Infinite Dilution: Structural Aspects

Calculation of the Microscopic and Macroscopic Linear and Nonlinear Optical Properties of Acetonitrile: I. Accurate Molecular Properties in the Gas Phase and Susceptibilities of the Liquid in Onsager's Reaction-Field Model

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