Replica method

The Helmholtz energy function of fluid in a matrix of configuration $\{{\mathbf {q} }^{N_{0}}\}$ in the Canonical ensemble is given by:

$-\beta A_{1}({\mathbf {q} }^{N_{0}})=\log Z_{1}({\mathbf {q} }^{N_{0}})=\log \left({\frac {1}{N_{1}!}}\int \exp[-\beta (H_{11}({\mathbf {r} }^{N_{1}})+H_{10}({\mathbf {r} }^{N_{1}},{\mathbf {q} }^{N_{0}}))]~d\{{\mathbf {r} }\}^{N_{1}}\right)$

where $Z_{1}({\mathbf {q} }^{N_{0}})$ is the fluid partition function, and $H_{11}$, $H_{10}$ and $H_{00}$ 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 $H_{00}$, we can average over matrix configurations to obtain

$-\beta {\overline {A}}_{1}={\frac {1}{N_{0}!Z_{0}}}\int \exp[-\beta _{0}H_{00}(q^{N_{0}})]~\log Z_{1}(q^{N_{0}})~d\{q\}^{N_{0}}$

(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

$\log x=\lim _{s\rightarrow 0}{\frac {\rm {d}}{{\rm {d}}s}}x^{s}$.

One can apply this trick to the $\log Z_{1}$ we want to average, and replace the resulting power $(Z_{1})^{s}$ 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 s} copies of the expression for 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_1} (replicas). The result is equivalent to evaluate 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 \overline{A}_1} as

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\to 0}\frac{d}{ds}\left(\frac{Z^{\rm rep}(s)}{Z_0}\right) } ,

where 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^{\rm rep}(s)} is the partition function of a mixture with Hamiltonian

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 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^{N_1}_\lambda, q^{N_0}) + H_{11}^\lambda (r^{N_1}_\lambda, q^{N_0})\right).}

This Hamiltonian describes a completely equilibrated system of $s+1$ components; the matrix the 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 s} 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) ] } .

References

1. S F Edwards and P W Anderson "Theory of spin glasses",Journal of Physics F: Metal Physics 5 pp. 965-974 (1975)
2. S F Edwards and R C Jones "The eigenvalue spectrum of a large symmetric random matrix", Journal of Physics A: Mathematical and General 9 pp. 1595-1603 (1976)