1549380323-Statistical Mechanics Theory and Molecular Simulation

(jair2018) #1

468 The Feynman path integral


ρ(x,x′;β) =

∫x(β ̄h)=x′

x(0)=x

Dx(τ) exp

[



1


̄h

∫β ̄h

0


(


1


2


mx ̇^2 +

1


2


mω^2 x^2

)]


. (12.4.18)


As we have already seen, paths in the vicinity of the classical path onthe inverted
potential dominate the functional integral. Thus, in order to perform the functional
integral, we utilize a technique known asexpansion about the classical path. Suppose
we are able to solve eqn. (12.4.14) for a classical pathxcl(τ) satisfyingxcl(0) =xand
xcl(β ̄h) =x′. Given this path, we perform a “change of variables” in the functional
integral; that is, we change the function of integrationx(τ) to a new functiony(τ) via
the transformation


x(τ) =xcl(τ) +y(τ). (12.4.19)

Eqn. (12.4.19) is similar to a change of variables of the formx=a+yin an ordinary
integral



f(x)dx, whereais a constant, so that dx= dy. Here, sincexcl(τ) is a single
function, it is analogous to the constanta, andDx(τ) =Dy(τ). For the harmonic
oscillator,xcl(τ) satisfies the classical equation of motion on the inverted potential
surface−U(x) =−mω^2 x^2 / 2


mx ̈cl=mω^2 xcl, (12.4.20)

withxcl(0) =xandxcl(β ̄h) =x′. Consequently,y(0) =y(β ̄h) = 0.
Substitution of this change of variables into the action integral yields


S=


∫β ̄h

0


[


1


2


mx ̇^2 +

1


2


mω^2 x^2

]


=


∫β ̄h

0


[


1


2


m( ̇xcl+ ̇y)^2 +

1


2


mω^2 (xcl+y)^2

]


=


∫β ̄h

0


[


1


2


mx ̇^2 cl+

1


2


mω^2 x^2 cl

]


+


∫β ̄h

0


[


1


2


my ̇^2 +

1


2


mω^2 y^2

]


+


∫β ̄h

0


[


mx ̇cly ̇+mω^2 xcly

]


. (12.4.21)


The last line of eqn. (12.4.21) contains cross terms betweenxcl(τ) andy(τ), but these
terms can be shown to vanish using an integration by parts:


∫β ̄h

0


[


mx ̇cly ̇+mω^2 xcly

]


=mx ̇cly





β ̄h

0

+


∫β ̄h

0


[


−mx ̈cl+mω^2 xcl

]


y

= 0. (12.4.22)


The boundary term vanishes becausey(0) =y(β ̄h) = 0, and the second term vanishes
becausexcl(τ) satisfies eqn. (12.4.20).

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