Replica method
The Helmholtz energy function of fluid in a matrix of configuration Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle \{{\mathbf {q} }^{N_{0}}\}} in the Canonical ensemble is given by:
- Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle -\beta A_{1}({\mathbf {q} }^{N_{0}})=\log Z_{1}({\mathbf {q} }^{N_{0}})=\log \left({\frac {1}{N_{1}!}}\int \exp[-\beta (H_{11}({\mathbf {r} }^{N_{1}})+H_{10}({\mathbf {r} }^{N_{1}},{\mathbf {q} }^{N_{0}}))]~d\{{\mathbf {r} }\}^{N_{1}}\right)}
where is the fluid partition function, and , and are the pieces of the Hamiltonian corresponding to the fluid-fluid, fluid-matrix and matrix-matrix interactions. Assuming that the matrix is a configuration of a given fluid, with interaction hamiltonian , we can average over matrix configurations to obtain
(see Refs. 1 and 2)
- An important mathematical trick to get rid of the logarithm inside of the integral is to use the mathematical identity
- .
One can apply this trick to the Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle \log Z_{1}} we want to average, and replace the resulting power by copies of the expression for (replicas). The result is equivalent to evaluate Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle {\overline {A}}_{1}} as
- ,
where Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle Z^{\rm {rep}}(s)} is the partition function of a mixture with Hamiltonian
- Failed to parse (Conversion error. Server ("https://wikimedia.org/api/rest_") reported: "Cannot get mml. Server problem."): {\displaystyle \beta H^{\rm {rep}}(r^{N_{1}},q^{N_{0}})={\frac {\beta _{0}}{\beta }}H_{00}(q^{N_{0}})+\sum _{\lambda =1}^{s}\left(H_{01}^{\lambda }(r_{\lambda }^{N_{1}},q^{N_{0}})+H_{11}^{\lambda }(r_{\lambda }^{N_{1}},q^{N_{0}})\right).}
This Hamiltonian describes a completely equilibrated system of components; the matrix the identical non-interacting replicas of the fluid. Since Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z_0=Z^{\rm rep}(0)} , then
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \lim_{s\to 0}\frac{d}{ds}[-\beta A^{\rm rep}(s)]=\lim_{s\to 0}\frac{d}{ds}\log Z^{\rm rep}(s)=\lim_{s\to 0}\frac{\frac{d}{ds}Z^{\rm rep}(s)}{Z^{\rm rep}(s)}=\lim_{s\to 0}\frac{\frac{d}{ds}Z^{\rm rep}(s)}{Z_0}=-\beta\overline{A}_1.}
Thus the relation between the Helmholtz energy function of the non-equilibrium partially frozen system and the replicated (equilibrium) system is given by
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle - \beta \overline{A}_1 = \lim_{s \rightarrow 0} \frac{{\rm d}}{{\rm d}s} [- \beta A^{\rm rep} (s) ] } .
Interesting reading
- Viktor Dotsenko "Introduction to the Replica Theory of Disordered Statistical Systems", Collection Alea-Saclay: Monographs and Texts in Statistical Physics, Cambridge University Press (2000)