Liouvilles Theorem

({p, q}) behaves like an incompressible uid.

3N
3
d

dpi
dqi

=
+
+
= 0
dt
t
qi dt
i=1 pi dt

Using Hamiltons equations this becomes

3N
3

H
H

t
qi pi

i=1 pi qi

8.044 L7B1

If the density in phase space depends only on the

energy at that point,
({p, q}) = (H{p, q}),

carrying out the indicated derivatives shows that

= 0.
t
This proves that = (H{p, q}) is a sucient con
dition for an equilibrium probability density in phase
space.
8.044 L7B2

1. The System
1. The System

E < energy < E+

<< E
Fixed:
E
V
N
M or H
P or E

A complete set of
independent thermodynamic
variables is fixed.
Many micro-states
satisfy the conditions.

8.044 L13B1
8.044
L7B3

2. Probability Density

All accessible microscopic states are equally probable.

Classical
p({p, q}) = 1/
= 0

accessible

E < H({p, q}) E +

elsewhere
{dp, dq} = (E, V, N )

8.044 L7B4

Quantum
p(k) = 1/
= 0

E < (k|H|k) E +
elsewhere

(1) = (E, V, N )

k, accessible

8.044 L7B5

Let X be a state of the system specied by a subset

{ p,q } of { p,q}
p(X) =

except {p"" ,q "" }

p({p, q}) {dp, dq}

1
=
{dp, dq}
""
""
except {p ,q }
"(consistent with X)
=

volume consistent with X

=
total volume of accessible phase space

8.044 L7B6

3. Quantities Related to

(E, V, N )

H({p,q})<E

{dp, dq}

= cumulative volume in phase space

(E, V, N )
(E, V, N )
E
= density of states as a function of energy

(E, V, N ) = (E, V, N )

8.044 L7B7

Example Ideal Monatomic Gas

qi = x, y, z
pi = mx,
my,
mz

N atoms

in a box

V = LxLy Lz
< pi <

pi2
H({p, q}) =
i=1 2m
3N

8.044 L7B8

{dp, dq} =

{dq} {dp}

N
Ly

Lx

dx

= VN

E<H<E+

dy

N
Lz

dz

{dp}

{dp}

(E, V, N ) =

VN

H<E

{dp}

8.044 L7B9

pi2
E=
i=1 2m
3N
3

2mE =

3N
3

p2
i

i=1

This describes a 3N dimensional spherical surface

in the p part of phase space with a radius R =

2mE.

8.044 L7B10

Math:
Volume of an dimensional sphere of radius R is
/2
R
(/2)!

Sterlings approximation for large M

ln(M !) M ln M M
M
M!
e

8.044 L7B11

3N/2

(E, N, V ) = V N
(2mE)3N/2
(3N/2)!

3N/2

4emE

3N

3N 1

{ }

2 E

(E, N, V ) =

3N

{ }

2 E

(E, N, V ) =

8.044 L7B12

'
V N 1Ly Lz
1
p(xi) =
=
=
N

V
Lx

0 x < Lx

'
V N 2Ly Lz LxLz
1
p(xi, yj ) =
=
=
= p(xi)p(yj ) S.I.

V
LxLy

p(pxi ) =

'
p({p,
q}){
dp , dq} =

p=

p
1/
xi

Note that ' diers on each of the three lines, be

ing a generic symbol for the reduced phase volume
consistent with some constraint.
8.044 L7B13

E p2
x /2m

EE distributed over other variables

(3N 1)/2

3N 1
4em(E E)
N

=
V
2
EE
3N 1

I
3N 1
E
4em 1/2
=

3N , E E
3
,
1

(N

3
N
1
2 +2
1
)

3N
N 2

(E

3N 1
E) 2 2

3N
E 2

8.044 L7B14

A =
N

but

3N

lim 1 + x

so A

3N
2

1
=
N

3N

1/2
+

3N/2

= ex

N e1/2

8.044 L7B15

B =

EE

E
1

3N

EE

1 E/

1
2

<E
3N/2

3N

> 2

where we have used < E > E/3N and E = 3N <

E >.
so B 1

3N <E>

eE/2<E>

8.044 L7B16

3
1
1/2
1/2

N e
p(px) =
e
eE/2<E>
3N < E >
4m

1
=
eE/2<E>
4m < E >

2
Now use E = p2
x /2m and < E >=< px > /2m.

p(px) =

1
2 < p2
x >

2 /2<p2 >
p
x
e x

8.044 L7B17

MIT OpenCourseWare
http://ocw.mit.edu

8.044 Statistical Physics I

Spring 2013

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