Replica method
The Helmholtz energy function of fluid in a matrix of configuration in the Canonical () ensemble is given by:
where is the fluid partition function, and is the Hamiltonian of the matrix. Taking an average over matrix configurations gives
(Ref.s 1 and 2) An important mathematical trick to get rid of the logarithm inside of the integral is
one arrives at
The Hamiltonian written in this form describes a completely equilibrated system of components; the matrix and identical non-interacting copies (replicas) of the fluid. Thus the relation between the Helmholtz energy function of the non-equilibrium partially frozen and the replica (equilibrium) system is given by
- .