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 19: Line 19:
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(r)\over{\delta \ln z(r')}}=\rho^{(2)}(r,r')-\rho(r)\rho(r')+\delta(r-r')\rho(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(r)\over{\delta\rho(r')}}={\delta(r-r')\over{\rho(r')}}  -c(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,

Revision as of 14:58, 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}),

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.