Transition state theory applied to self-diffusion of hard spheres

A description in terms of transition rates among cells is used to analyze self-diffusion of hard spheres in the fluid phase. Cell size is assumed much larger than the mean free path. Transition state theory is used to obtain an equation that matches numerical results previously obtained by other authors. Two regimes are identified. For small packing fraction $\xi$, diffusion is limited by free volume; and, for large $\xi$, diffusion is limited by velocity autocorrelation. The expressions obtained in each regime do not require adjustable parameters.

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