Rare Events and Free Energy Landscapes

Within classical nucleation theory the free energy of the system as a function of the radius r of a spherical crystallite can be expressed as 

Transition path sampling can also be helpful in the calculation of free energies in the context of fast-switching methods described in Chap. 5. As shown by Jarzynski [12], equilibrium free energies can be computed from the work performed on a system in repeated transformations carried out arbitrarily far from equilibrium. From a computational point of view, this remarkable theorem is attractive because it promises efficient free energy calculations due to the reduced cost of 

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