Bagchi, Biman (1991) Microscopic expression for dielectric friction on a moving ion. In: Journal of Chemical Physics, 95 (1). pp. 467-78.
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A theoretical study of the dielectric friction on an ion moving through a dipolar liquid is presented. A microscopic expression for the dielectric friction is derived from linear response theory for a Brownian ion. This expression supports the picture of a "dynamic solventberg" model in the sense that much of the contribution to dielectric friction $(\zeta_DF)$ comes from the nearest-neighbor molecules. The translational modes of the solvent are found to have a very strong influence on the dielectric friction, in agreement with the observation of Colonomos and Wolynes [J. Chem. Phys. 71,2644 (1979)]. In fact, except in the limit of small ion size, the microscopic $\zeta_DF$ is significantly larger than the continuum $\zeta_DF$ in the absence of the translational motion of the solvent molecules, but the reverse is obtained in the presence of a substantial translational contribution. It is found that the recovery of the continuum limit results from the molecular expression requires serious assumptions, some of which are hard to justify. It is also found that the point dipole approximation for the dipolar solvent molecule leads to improper results for $\zeta_DF$ because this approximation gives a wrong wave vector (k) dependence of the wave vector dependent dielectric function $(\epsilon(k))$ of the liquid at large k $(k\sigma\gg 2\pi$, where $\sigma$ is the solvent molecular diameter). We show that within a linear equilibrium theory for dipolar liquids, the cross correlations between the short ranged hard force and the long ranged dipolar force is zero so the calculations of Colonomos and Wolynes are internally consistent. However, this cross correlation can be quite important if the soft force also contains a spherically symmetric part. The similarity between the solvent role in $\zeta_DF$ and in the time-dependent fluorescence Stokes shift is discussed. The limitations of the present theory are also pointed out.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this artile belongs to American Institute of Physics.|
|Department/Centre:||Division of Chemical Sciences > Solid State & Structural Chemistry Unit|
|Date Deposited:||22 Aug 2008|
|Last Modified:||16 Jan 2012 04:54|
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