A transition state theory for calculating hopping times and diffusion in highly confined fluids.

ABSTRACT

Monte Carlo simulation is used to study the dynamical crossover from single file diffusion to normal diffusion in fluids confined to narrow channels. We show that the long time diffusion coefficients for a series of systems involving hard and soft interaction potentials can be described in terms of a hopping time that measures the time it takes for a particle to escape the cage formed by its neighbors in the pore. Free energy barriers for the particle hopping process are calculated and used to show that transition state theory effectively describes the hopping time for all the systems studied over a range of pore radii. Our work suggests that the combination of hopping times and transition state theory offers a useful and general framework to describe the dynamics of highly confined, single file fluids.