# Comment on “Diffusion of Ionic Particles in Charged Disordered Media”

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In a recent Letter, Mehrabi and Sahimi discuss motion of ions in charged disordered media, presenting a variety of results obtained by Monte Carlo simulation on a lattice . Their observations of mean square displacements $`R^2(t)`$ suggest that this model exhibits anomalous diffusion in three dimensions:

$$R^2(t)(\mathrm{c}onst)t^{1\delta }\mathrm{a}st\mathrm{}.$$
(1)   
They observe the same behavior in one and two dimensions, but do not present results for $`\delta `$. Mehrabi and Sahimi also make the physically-surprising claim that a suitably-defined “short-time diffusivity” can actually *increase* with increasing disorder strength (see Fig. 3 of Ref. ). Exact bounds, renormalization group calculations, and previous numerical simulations are inconsistent with these results in three dimensions.

At low concentrations of mobile ions, the Green function for a diffusing ion should obey the diffusion equation:

$$\frac{c_v(𝐫,t)}{t}=D_0^2c_v+\beta D_0[c_vv(𝐫)].$$
(2)   
Here $`c_v`$ is the Green function of a single ion in a given realization of the quenched random potential $`v`$, $`D_0`$ is the “bare,” short-time diffusivity, and $`\beta `$ is the inverse temperature. The mean square displacement is given by $`R_v^2(t)=d^d𝐫|𝐫|^2c_v(𝐫,t)`$. The observable mean square displacement is given by an average over all realizations of the disorder: $`R^2(t)=R_v^2(t)`$. The effective diffusion diffusion coefficient is defined in $`d`$ dimensions by $`D=lim_t\mathrm{}R^2(t)/(2dt)`$.

Mehrabi and Sahimi model the disorder by a quenched Gaussian random potential field. The statistics of this potential field are chosen so that they obey bulk charge neutrality: $`\widehat{\chi }_{vv}(𝐤)=\gamma /[k^2(k^2+\kappa ^2)]`$. Here the potential-potential correlation function is $`\chi _{vv}(𝐫)=v(\mathrm{𝟎})v(𝐫)`$, $`\kappa `$ is an inverse correlation length, and $`\gamma `$ is a measure of the density of defects. The Fourier transform in $`d`$ dimensions is given by $`\widehat{f}(𝐤)=d^d𝐫f(𝐫)\mathrm{exp}(i𝐤𝐫)`$.

The single-ion, random diffusion model is a well-studied one in statistical physics, and a variety of exact results are known. First, there is an exact bound for the diffusivity in this system in any dimension :

$$\frac{D}{D_0}\mathrm{exp}[\beta ^2\chi _{vv}(0)].$$
(3)   
Calculating this bound in three dimensions, one finds $`D/D_0\mathrm{exp}[\beta ^2\gamma /(4\pi \kappa )]`$. This result implies that the motion is diffusive in three dimensions, *i.e.* $`D>0`$. The motion is also diffusive at finite ion concentrations, since the dynamical exponent is 2 . Therefore, the motion should be asymptotically diffusive in three dimensions. Indeed, previous careful simulations by Dean, Drummond, and Horgan on related models have confirmed the bound . Moreover, these simulations have shown that Deem and Chandler’s single-ion prediction 

$$\frac{D}{D_0}=\mathrm{exp}[\beta ^2\chi _{vv}(0)/d]$$
(4)   
is accurate to at least moderate disorder strengths. In fact, this equation is correct to second order in $`\beta ^2\chi _{vv}(0)`$ in all dimensions and is exact in one dimension. Note that, as expected physically, the diffusion constant *decreases* with increasing disorder strength.

The situation is more interesting in two dimensions, where anomalous diffusion can occur \[the bound in Eq. (3) vanishes\]. Indeed, field-theoretic treatments have shown that the exponent in Eq. (1) is continuously variable and is given exactly by $`\delta =1/[1+8\pi \kappa ^2/(\beta ^2\gamma )]`$ . This scaling has been confirmed by numerical simulations . At finite ion concentrations, the anomalous diffusion persists at high temperature , although the mobile ions may partially screen the disorder. A Kosterlitz-Thouless transition can occur at low temperature .