1549380323-Statistical Mechanics Theory and Molecular Simulation

(jair2018) #1

148 Canonical ensemble


Q(N,V,T,r,r′) =

1


h^3 N


dNpdNrexp

{


−β

[N



i=1

p^2 i
2 m

+


1


2


mω^2

∑N


i=0

(ri−ri+1)^2

]}


. (4.5.23)


We will regard the particles as truly distinguishable so that no 1/N! is needed. The
Gaussian integrals over theNmomenta can be performed immediately, yielding


Q(N,V,T,r,r′) =

1


h^3 N

(


2 πm
β

) 3 N/ 2 ∫


dNrexp

[



1


2


βmω^2

∑N


i=0

(ri−ri+1)^2

]


. (4.5.24)


The coordinate integrations can be performed straightforwardly, if tediously, by simply
integrating first overr 1 , then overr 2 ,... and recognizing the pattern that results after
n < Nsuch integrations have been performed. We will first follow this procedure, and
then we will show how a simple change of integration variables can be used to simplify
the integrations by uncoupling the harmonic interaction term.
Consider, first, the integration overr 1. Definingα=βmω^2 /2, and using the fact
thatV is much larger than the average nearest-neighbor particle distance to extend
the integration over all space, the integral that must be performed is


I 1 =


all space

dr 1 e−α[(r^1 −r)

(^2) +(r 2 −r 1 ) (^2) ]


. (4.5.25)


Expanding the squares gives


I 1 = e−α(r

(^2) +r (^22) )



all space

dr 1 e−^2 α[r

(^21) −r 1 ·(r+r 2 )]


. (4.5.26)


Now, we can complete the square to give


I 1 = e−α(r

(^2) +r (^22) )
eα(r+r^2 )
(^2) / 2



all space

dr 1 e−^2 α[r^1 −(r+r^2 )/2]

2

= e−α(r^2 −r)

(^2) / 2 (π
2 α


) 3 / 2


. (4.5.27)


We can now proceed to ther 2 integration, which is of the form


I 2 =


2 α

) 3 / 2 ∫


all space

dr 2 e−α(r^2 −r)

(^2) / 2
e−α(r^3 −r^2 )
2


. (4.5.28)


Again, we begin by expanding the squares to yield


I 2 =



2 α

) 3 / 2


e−α(r

(^2) +2r (^23) )/ 2



all space

dr 2 e−^3 α[r

(^22) − 2 r 2 ·(r+2r 3 )/3]/ 2


. (4.5.29)


Completing the square gives

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