Ornstein-Zernike relation from the grand canonical distribution function: Difference between revisions

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Using those definitions the [[grand canonical partition function]] can be written as
Using those definitions the [[grand canonical partition function]] can be written as


<math>\Xi=\sum_N^\infty{1\over N!}\int\dots\int \prod_i^Nz( r_i)\exp(-\beta U_N)dr_1\dots dr_N.</math>
:<math>\Xi=\sum_N^\infty{1\over N!}\int\dots\int \prod_i^Nz( r_i)\exp(-\beta U_N)dr_1\dots dr_N</math>.


By functionally-differentiating <math>\Xi</math>  with respect to <math>z(r)</math>, and utilizing the mathematical theorem concerning the functional derivative,
By functionally-differentiating <math>\Xi</math>  with respect to <math>z(r)</math>, and utilizing the mathematical theorem concerning the functional derivative,


<math>{\delta z(r)\over{\delta z(r')}}=\delta(r-r'),</math>
:<math>{\delta z(r)\over{\delta z(r')}}=\delta(r-r')</math>,


we get the following equations with respect to the density pair correlation functions.
we get the following equations with respect to the density pair correlation functions.


<math>\rho({\bf r})={\delta\ln\Xi\over{\delta \ln z({\bf r})}},</math>
:<math>\rho(r)={\delta\ln\Xi\over{\delta \ln z(r)}}</math>,




<math>\rho^{(2)}({\bf r,r'})={\delta^2\ln\Xi\over{\delta \ln z({\bf r})\delta\ln z({\bf r'})}}.</math>
:<math>\rho^{(2)}(r,r')={\delta^2\ln\Xi\over{\delta \ln z(r)\delta\ln z(r')}}</math>.


A relation between <math>\rho(r)</math> and <math>\rho^{(2)}(r,r')</math> can be obtained after some manipulation as,
A relation between <math>\rho(r)</math> and <math>\rho^{(2)}(r,r')</math> can be obtained after some manipulation as,


<math>{\delta\rho({\bf r})\over{\delta \ln z({\bf r'})}}=\rho^{(2)}({\bf r,r'})-\rho({\bf r})\rho({\bf r'})+\delta({\bf r}-{\bf r'})\rho({\bf r}).</math>
:<math>{\delta\rho({\bf r})\over{\delta \ln z({\bf r'})}}=\rho^{(2)}({\bf r,r'})-\rho({\bf r})\rho({\bf r'})+\delta({\bf r}-{\bf r'})\rho({\bf r}).</math>


Now, we define the direct correlation function by an inverse relation of Eq. (\ref{deltarho}),
Now, we define the direct correlation function by an inverse relation of Eq. (\ref{deltarho}),


<math>{\delta \ln z({\bf r})\over{\delta\rho({\bf r'})}}={\delta({\bf r}-{\bf r'})\over{\rho({\bf r'})}}  \label{deltalnz}-c({\bf r,r'}).</math>
:<math>{\delta \ln z({\bf r})\over{\delta\rho({\bf r'})}}={\delta({\bf r}-{\bf r'})\over{\rho({\bf r'})}}  \label{deltalnz}-c({\bf r,r'}).</math>


Inserting Eqs. (\ref{deltarho}) and (\ref{deltalnz}) into the chain-rule theorem of functional derivatives,
Inserting Eqs. (\ref{deltarho}) and (\ref{deltalnz}) into the chain-rule theorem of functional derivatives,


<math>\int{\delta\rho({\bf r})\over{\delta \ln z({\bf r}^{\prime\prime})}}{\delta \ln z({\bf r}^{\prime\prime})\over{\delta\rho({\bf r'})}}{\rm d}{\bf r}^{\prime\prime}=\delta({\bf r}-{\bf r'}),</math>
:<math>\int{\delta\rho({\bf r})\over{\delta \ln z({\bf r}^{\prime\prime})}}{\delta \ln z({\bf r}^{\prime\prime})\over{\delta\rho({\bf r'})}}{\rm d}{\bf r}^{\prime\prime}=\delta({\bf r}-{\bf r'}),</math>


one obtains the [[Ornstein-Zernike relation]].
one obtains the [[Ornstein-Zernike relation]].

Revision as of 14:56, 27 February 2007

Defining the local activity by where , and is the Boltzmann constant. Using those definitions the grand canonical partition function can be written as

.

By functionally-differentiating with respect to , and utilizing the mathematical theorem concerning the functional derivative,

,

we get the following equations with respect to the density pair correlation functions.

,


.

A relation between and can be obtained after some manipulation as,

Now, we define the direct correlation function by an inverse relation of Eq. (\ref{deltarho}),

Failed to parse (unknown function "\label"): {\displaystyle {\delta \ln z({\bf r})\over{\delta\rho({\bf r'})}}={\delta({\bf r}-{\bf r'})\over{\rho({\bf r'})}} \label{deltalnz}-c({\bf r,r'}).}

Inserting Eqs. (\ref{deltarho}) and (\ref{deltalnz}) into the chain-rule theorem of functional derivatives,

one obtains the Ornstein-Zernike relation. Thus the Ornstein-Zernike relation is, in a sense, a differential form of the partition function.