Synthetic approach to alloy thermodynamics and kinetics by cluster variation method and path probability method

The cluster variation method of equilibrium thermodynamics is employed to calculate the Ll₀-disorder phase diagram. The stability analysis based on the second-order derivative of the free energy functional with respect to the deviation of correlation functions from their equilibrium values yields the 100 instability locus in the phase diagram. The time evolution of cluster probabilities at the phase transition is investigated on the basis of the path probability method of non-equilibrium statistical mechanics. Thereby the synthetic study of thermodynamics and kinetics based on the cluster variation method and the path probability method is attempted. It is shown that the fluctuation is necessary to drive the ordering reaction above the instability temperature, whereas the spinodal-like ordering transition takes place below the instability temperature. The extension of the present study of a spin system to an alloy system is briefly discussed and a critical problem to be settled is pointed out.