1549380323-Statistical Mechanics Theory and Molecular Simulation

(jair2018) #1

284 Monte Carlo


Eqn. (7.2.18) is a function ofyalone, and we can now analyze itsydependence in
greater detail. First, the extrema ofF( ̃σ(y),y) are given by the solution of


0 =

dF
dy

=


∂F


∂y

+


∂F


∂σ ̃

∂σ ̃
∂y
=−i ̃σ(y). (7.2.19)

Since∂F/∂ ̃σ(y) = 0 by the definition of ̃σ(y), the extrema ofFoccur where ̃σ(y) = 0.
According to eqn. (7.2.16), this implies


y=


dxφ(x)f(x)

dxf(x)

=〈φ〉f. (7.2.20)

Because this solution is unique, we can expandF( ̃σ(y),y) to second order abouty=
〈φ〉f. For this, we need
d^2 F
dy^2






̃σ=0

=−i
d ̃σ
dy





̃σ=0

. (7.2.21)


Differentiating eqn. (7.2.16) atσ= ̃σ(y) with respect toy, we obtain


1 =−ig′′( ̃σ)

d ̃σ
dy

, (7.2.22)


so that
d ̃σ
dy






̃σ=0

=


i
g′′(0)

. (7.2.23)


Note, however, that


g′′(0) =i

[∫


dxφ^2 (x)f(x)

dxf(x)


(∫


dxφ(x)f(x)

) 2


(∫


dxf(x)

) 2


]


=i

[


〈φ^2 〉f−〈φ〉^2 f

]


, (7.2.24)


which (apart from the factor ofi) is just the square of the fluctuationδφinφ(x) with
respect to the distributionf(x). From this analysis, we see thatP(y) has a single
maximum aty=〈φ〉fand decreases monotonically in either direction from this point.
In the limit thatM becomes very large, all higher-order contributions, which are
simply higher-order moments offwith respect toP(y), vanish, so thatP(y) becomes
just a Gaussian normal distribution


P(y)−→


M


2 πδφ^2

exp

[



M(y−〈φ〉f)^2
2 δφ^2

]


. (7.2.25)


We conclude, finally, that for largeM, eqn. (7.2.5) can be approximated via eqn.
(7.2.3) with a variance consistent with a normal distribution in the limit of largeM,
i.e.,



dxφ(x)f(x) =

1


M


∑M


i=1

φ(xi)±

1



M


[


〈φ^2 〉f−〈φ〉^2 f

] 1 / 2


=


∑M


i=1

φ(xi)±δφ, (7.2.26)

thus guaranteeing convergence in the limitM→∞. Since the variance (second) term
in eqn. (7.2.26), decreases as 1/



M, efficient convergence relies on making this vari-
ance as small as possible, which is one of the challenges in designing Monte Carlo

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