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General distribution functions and correlation functions

We begin by considering a general N-particle system with Hamiltonian

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For simplicity, we consider the case that all the particles are of the same type. Having established the equivalence of the ensembles in the thermodynamic limit, we are free to choose the ensemble that is the most convenient on in which to work. Thus, we choose to work in the canonical ensemble, for which the partition function is

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The 3N integrations over momentum variables can be done straighforwardly, giving

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where tex2html_wrap_inline135 is the thermal wavelength and the quantity tex2html_wrap_inline137 is known as the configurational partition function

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The quantity

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represents the probability that particle 1 will be found in a volume element tex2html_wrap_inline139 at the point tex2html_wrap_inline141 , particle 2 will be found in a volume element tex2html_wrap_inline143 at the point tex2html_wrap_inline145 ,..., particle N will be found in a volume element tex2html_wrap_inline149 at the point tex2html_wrap_inline151 . To obtain the probability associated with some number n;SPMlt;N of the particles, irrespective of the locations of the remaining n+1,...,N particles, we simply integrate this expression over the particles with indices n+1,...,N:

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The probability that any particle will be found in the volume element tex2html_wrap_inline139 at the point tex2html_wrap_inline141 and any particle will be found in the volume element tex2html_wrap_inline143 at the point tex2html_wrap_inline145 ,...,any particle will be found in the volume element tex2html_wrap_inline167 at the point tex2html_wrap_inline169 is defined to be

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which comes about since the first particle can be chosen in N ways, the second chosen in N-1 ways, etc.

Consider the specal case of n=1. Then, by the above formula,

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Thus, if we integrate over all tex2html_wrap_inline141 , we find that

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Thus, tex2html_wrap_inline179 actually counts the number of particles likely to be found, on average, in the volume element tex2html_wrap_inline139 at the point tex2html_wrap_inline141 . Thus, integrating over the available volume, one finds, not surprisingly, all the particles in the system.


next up previous
Next: About this document Up: Structure and distribution functions Previous: Structure and distribution functions

Mark Tuckerman
Mon Oct 6 13:38:31 EDT 1997