1549380323-Statistical Mechanics Theory and Molecular Simulation

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Path integral derivation 453

〈xk+1|e−β
K/Pˆ
|xk〉=


dp〈xk+1|p〉〈p|xk〉e−βp

(^2) / 2 mP


. (12.2.16)


Finally, using eqn. (9.2.43), eqn. (12.2.16) becomes


〈xk+1|e−β
K/Pˆ
|xk〉=

1


2 π ̄h


dpe−βp

(^2) / 2 mP
eip(xk+1−xk)/ ̄h. (12.2.17)
Since the range of the momentum integration isp∈(−∞,∞), the above integral is a
typical Gaussian integral that can be evaluated by completing the square. Thus, we
write
βp^2
2 mP



ip(xk+1−xk)
̄h

=


β
2 mP

[


p^2 −

2 imPp(xk+1−xk)
β ̄h

]


=


β
2 mP

{[


p−
imP(xk+1−xk)
β ̄h

] 2


+


m^2 P^2 (xk+1−xk)^2
β^2 ̄h^2

}


=


β
2 mP

[


p−
imP(xk+1−xk)
β ̄h

] 2


+


mP
2 β ̄h^2

(xk+1−xk)^2. (12.2.18)

When the two last lines of eqn. (12.2.18) are substituted back into eqn. (12.2.17), and
a change of variables


p ̃=p−

imP(xk+1−xk)
β ̄h

(12.2.19)


is made, we find


〈xk+1|e−β
K/Pˆ
|xk〉=

1


2 π ̄h

exp

[



mP
2 β ̄h^2

(xk+1−xk)^2

]∫∞


−∞

d ̃pe−βp ̃

(^2) / 2 mP


=


(


mP
2 πβ ̄h^2

) 1 / 2


exp

[



mP
2 β ̄h^2

(xk+1−xk)^2

]


. (12.2.20)


Now, eqn. (12.2.20) is combined with eqn. (12.2.13) to yield


〈xk+1|Ωˆ|xk〉=

(


mP
2 πβ ̄h^2

) 1 / 2


exp

[



β
2 P

(U(xk+1) +U(xk))

]


×exp

[



mP
2 β ̄h^2

(xk+1−xk)^2

]


. (12.2.21)


Finally, multiplying allP matrix elements together and integrating over theP− 1
coordinate variables, we obtain for the density matrix:

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