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

From SklogWiki
Jump to navigation Jump to search
No edit summary
No edit summary
Line 4: Line 4:
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({\b f r}_i)\exp(-\beta U_N){\rm d}{\bf r}_1\dots{\rm d}{\bf r}_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({\bf r})\over{\delta z({\bf r'})}}=\delta({\bf r}-{\bf 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.
Line 29: Line 29:
<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 equation]].
one obtains the [[Ornstein-Zernike relation]].
Thus the Ornstein-Zernike equation is,
Thus the Ornstein-Zernike relation is,
in a sense, a differential form of the partition function.
in a sense, a differential form of the partition function.


[[Category:Integral equations]]
[[Category:Integral equations]]

Revision as of 14:54, 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.