1549380323-Statistical Mechanics Theory and Molecular Simulation

(jair2018) #1

110 Microcanonical ensemble


ThatiL 1 andiL 2 donotgenerally commute can be seen in a simple one-dimensional
example. Consider the Hamiltonian


H=


p^2
2 m

+U(x). (3.10.12)

According to eqn. (3.10.9),


iL 1 =

p
m


∂x

, iL 2 =F(x)


∂p

, (3.10.13)


whereF(x) =−dU/dx. The action ofiL 1 iL 2 on a functionφ(x,p) is


p
m


∂x

F(x)


∂p

φ(x,p) =

p
m

F(x)

∂^2 φ
∂p∂x

+


p
m

F′(x)

∂φ
∂p

, (3.10.14)


whereas the action ofiL 2 iL 1 onφ(x,p) is


F(x)


∂p

p
m


∂x

φ(x,p) =F(x)

p
m

∂^2 φ
∂p∂x

+F(x)

1


m

∂φ
∂x

, (3.10.15)


so that [iL 1 ,iL 2 ]φ(x,p) is


[iL 1 ,iL 2 ]φ(x,p) =

p
m

F′(x)

∂φ
∂p


F(x)
m

∂φ
∂x

. (3.10.16)


Since the functionφ(x,p) is arbitrary, we can conclude that the operator


[iL 1 ,iL 2 ] =

p
m

F′(x)


∂p


F(x)
m


∂x

, (3.10.17)


from which it can be seen that [iL 1 ,iL 2 ] 6 = 0.
SinceiL 1 andiL 2 generally do not commute, the classical propagator exp(iLt) =
exp[(iL 1 +iL 2 )t]cannotbe separated into a simple product exp(iL 1 t) exp(iL 2 t). This is
unfortunate because in many instances, the action of the individual operators exp(iL 1 t)
and exp(iL 2 t) on the phase space vector can be evaluated exactly. Thus, it would be
useful if the propagator could somehow be expressed in terms of these two factors.
In fact, there is a way to do this using an important theorem known as theTrotter
theorem(Trotter, 1959). This theorem states that given two operatorsAandBfor
which [A,B] 6 = 0,


eA+B= lim
P→∞

[


eB/^2 PeA/PeB/^2 P

]P


, (3.10.18)


wherePis an integer. In fact, eqn. (3.10.18) is commonly referred to as thesymmetric
Trotter theoremorStrang splitting formula(Strang, 1968). The proof of the Trotter

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