1549380323-Statistical Mechanics Theory and Molecular Simulation

(jair2018) #1

94 Microcanonical ensemble


The partition function is

Ω(E) =


E 0


h

∫∞


−∞

dp

∫∞


−∞

dx δ

(


p^2
2 m

+


1


2


kx^2 −E

)


. (3.6.3)


In order to evaluate the integral in eqn. (3.6.3), we first introducea change of variables


p ̃=

p

2 m

x ̃=


k
2

x, (3.6.4)

so that the partition function can be written as


Ω(E) =


E 0


h


m
k

∫∞


−∞

d ̃p

∫∞


−∞

d ̃x δ

(


̃p^2 + ̃x^2 −E

)


. (3.6.5)


Recall from Section 1.3, however, that



k/m=ωis just the fundamental frequency
of the oscillator. The partition function then becomes


Ω(E) =


E 0



∫∞


−∞

d ̃p

∫∞


−∞

d ̃x δ

(


p ̃^2 + ̃x^2 −E

)


. (3.6.6)


Theδ-function requires that ̃p^2 + ̃x^2 =E, which defines a circle in the scaled ( ̃p, ̃x)
phase space. Therefore, it is natural to introduce polar coordinates in the form


p ̃=


Iωcosθ

x ̃=


Iωsinθ. (3.6.7)

Here, the usual “radial” coordinate has been expressed as



Iω. The new coordinates
(I,θ) are known asaction-anglevariables. They are chosen such that the Jacobian is
simply a constant,ω, so that the partition function becomes


Ω(E) =


E 0


h

∫ 2 π

0


∫∞


0

dI δ(Iω−E). (3.6.8)

In action-angle variables, the harmonic Hamiltonian has the rather simple formH=
Iω. If one were to derive Hamilton’s equations in terms of action-angle variables, the
result would be simply,θ ̇=∂H/∂I=ωandI ̇=−∂H/∂θ= 0 so that the actionIis a
constantI(0) for all time, andθ=ωt+θ(0). The constancy of the action is consistent
with energy conservation;I∝E. The angle then gives the oscillatory time dependence
ofxandp. In eqn. (3.6.8), the angular integration can be performed directlyto yield


Ω(E) =


2 πE 0
h

∫∞


0

dI δ(Iω−E). (3.6.9)

Changing the action variable toI′=Iω, we obtain


Ω(E) =


E 0


̄hω

∫∞


0

dI′δ(I′−E), (3.6.10)
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