Generalized Smoluchowski equation with correlation between clusters

Abstract

In this paper we compute new reaction rates of the Smoluchowski equation which takes into account correlations. The new rate K = KMF + KC is the sum of two terms. The first term is the known Smoluchowski rate with the mean-field approximation. The second takes into account a correlation between clusters. For this purpose we introduce the average path of a cluster. We relate the length of this path to the reaction rate of the Smoluchowski equation. We solve the implicit dependence between the average path and the density of clusters. We show that this correlation length is the same for all clusters. Our result depends strongly on the spatial dimension d. The mean-field term KMFi,j = (Di + Dj)(rj + ri)d-2, which vanishes for d = 1 and is valid up to logarithmic correction for d = 2, is the usual rate found with the Smoluchowski model without correlation (where ri is the radius and Di is the diffusion constant of the cluster). We compute a new rate: the correlation rate Ki,jC (Di+Dj)(rj+ri)d-1M(d-1df) is valid for d ≤ 1(where M(α) = Σ+∞ i=1iαNi is the moment of the density of clusters and df is the fractal dimension of the cluster). The result is valid for a large class of diffusion processes and mass radius relations. This approach confirms some analytical solutions in d 1 found with other methods. We also show Monte Carlo simulations which illustrate some exact new solvable models.

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