1549380323-Statistical Mechanics Theory and Molecular Simulation

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Examples of frequency spectra 549

(Shankar, 1994), where the action of ˆaand ˆa†on an energy eigenstate of the oscillator
is
aˆ|n〉=



n|n− 1 〉, aˆ†|n〉=


n+ 1|n+ 1〉. (14.4.2)

These operators satisfy the commutation relation [ˆa,ˆa†] = 1. In terms of the creation
and annihilation operators, the Hamiltonian for a harmonic oscillator of frequencyω 0
can be written as


Hˆ 0 =

(


aˆ†ˆa+

1


2


)


̄hω 0. (14.4.3)

In the interaction picture, the operators ˆaand ˆa†evolve according to the equations of
motion


dˆa
dt

=


1


i ̄h

[ˆa,Hˆ 0 ] =−iω 0 aˆ

dˆa†
dt

=


1


i ̄h

[ˆa†,Hˆ 0 ] =iω 0 ˆa†. (14.4.4)

Eqns. (14.4.4) are readily solved to yield


aˆ(t) = ˆae−iω^0 t, ˆa†(t) = ˆa†eiω^0 t. (14.4.5)

Using eqn. (10.4.19), the correlation function〈xˆ(0)ˆx(t)〉can be written as


〈ˆx(0)ˆx(t)〉=

̄h
2 mω 0

1 −e−β ̄hω^0
e−β ̄hω^0 /^2

×


∑∞


n=0

e−(n+1/2)β ̄hω^0 〈n|(ˆa+ ˆa†)(ˆae−iω^0 t+ ˆa†eiω^0 t)|n〉. (14.4.6)

After some algebra, we find that


〈xˆ(0)ˆx(t)〉=

̄h
4 mω 0 sinh(β ̄hω 0 /2)

[


eiω^0 teβ ̄hω^0 /^2 + e−iω^0 te−β ̄hω^0 /^2

]


. (14.4.7)


Similarly, the correlation function〈xˆ(t)ˆx(0)〉can be shown to be


〈xˆ(t)ˆx(0)〉=

̄h
4 mω 0 sinh(β ̄hω 0 /2)

[


e−iω^0 teβ ̄hω^0 /^2 + eiω^0 te−β ̄hω^0 /^2

]


. (14.4.8)


When we combine eqns. (14.4.7) and (14.4.8), the symmetric correlation function is
found to be
1
2



[ˆx(0),ˆx(t)]+


=


̄h
2 mω 0

tanh(β ̄hω 0 /2) cos(ω 0 t). (14.4.9)

A comparison of eqn. (14.4.9) and eqn. (13.3.39) reveals that the quantum and classical
correlation functions are related by


1
2


[ˆx(0),ˆx(t)]+


=


β ̄hω 0
2

tanh(β ̄hω 0 /2)〈x(0)x(t)〉cl. (14.4.10)

The connection established in eqn. (14.4.10) between the quantum and classical posi-
tion autocorrelation functions of a harmonic oscillator can be exploited as a method

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