6

U Z
S= + kB N ln + kB N.
T N
dN = 0

dU U
dS = − 2 dT + kB N d ln Z.
T T

T
¯ = T dS
dQ

U
¯ = dU −
dQ dT + N kB T d ln Z.
T

¯ = dU + P dV
dQ

U
N kB T d ln Z = dT + P dV.
T

∂
U = N kB T 2 ln Z,
∂T

106
 P = N kB T
∂
∂V
ln Z. 6

Z = V (2πmkB T )3/2 ,

3 3
U = N kB T, U = N RT.
2 2

P V = N kB T, P V = N RT,

N/V

N kB T
P ≈ .
V

N/V

107
 N kB T N2 N3 N4
P = + A 2 + B 3 + C 4 + ···
V V V V

A B C

... ∗

 
pi , ri }N
E({ i=1 ) = K(
pi ) + U (ri , rj ).
i i<j

p2i
Ki ≡ K(
pi ) =
2m

i pi

Uij ≡ U(ri , rj )

i ri j rj

 
E= Ki + Uij .
i i<j

108
 i<j i = j 6
i
j j i Uij = Uji

Uij = U12 + U13 + · · · + U23 + · · · .
i<j

 ∞  
 3
Z= d d r d3 pδ[ − (r, p)] exp(−β ).
0

 
Z= d3r d3 p exp[−β(r, p)],

exp[−β(r, p)] (r, p)

   
1 3 3 3
Z= d r1 d p1 · · · d rN d3 pN exp[−βE({
pi , ri }N
i=1 )].
N!

109
 N!

⎛ ⎞
N 
 
1 ⎝
Z= d3rj d3 pj ⎠ exp(−βE),
N!
j=1

E =
1 + · · · + N
⎛ ⎞
N   N
1 ⎝ 
Z = d3rj d3 pj ⎠ exp −β i
N!
j=1 i=1
⎛ ⎞
N   N
1 ⎝ 
= d3rj d3 pj ⎠ exp(−βi )
N!
j=1 i=1
N  
1 
= d3rj d3 pj exp(−βj )
N!
j=1
N
1 
= Zj
N!
j=1

Zj j
Zj = Z
j

ZN
Z= .
N!

110
 6
∂
U = kB T 2 ln Z,
∂T

∂
P = kB T ln Z.
∂V

⎛ ⎞ ⎡ ⎛ ⎞⎤
    
1 ⎝
Z = d3rj d3 pj ⎠ exp ⎣−β ⎝ Ki + Uij ⎠⎦ ,
N!
j i i<j
  ⎡ 
⎤
1   
= d3 pk exp (−βKk ) ⎣ d3rl exp (−βUij )⎦
N!
k l i<j
 N  
1 Z
= d3rl exp (−βUij )
N! V
l i<j

ZN 1  
= d3rl exp (−βUij )
N! VN
l i<j

Z
d3 pi (2πmkB T )3/2 = Z /V N
k
N

Z=Z Z

VN
Z = (2πmkB T )3N/2 ,
N!


1  
Z = d3rl exp (−βUij ) .
VN
l i<j

111
 Uij Z

1
exp (−βUij ) = 1 − βUij + β 2 Uij2 + · · · = 1 + fij ,
2

∞
 1
fij ≡ (−βUij )k = exp (−βUij ) − 1
k!
k=1

Uij  kB T βUij  1

112
 fij  1 6

  
exp (−βUij ) = (1 + fij ) ≈ 1 + fij .
i<j i<j i<j

⎛ ⎞

1  ⎝1 +

Z ≈ d3rl fij ⎠
VN
l i<j
⎛ ⎞

1  ⎝

= 1+ d3rl fij ⎠,
VN
l i<j
  
I1

V = d3ri
⎛ ⎞

1  
I1 ≡ N
d3rl ⎝ fij ⎠
V
l i<j
  
1 3 3
= d 
r1 d 
r 2 · · · d3rN (f12 + f13 + · · · + fN −1 N )
VN
     
1 3 3 3 3 3
= d r1 d r2 f12 d r3 d r4 · · · d rN +
VN
     
1 3 3 3 3 3
d r1 d r3 f13 d r2 d r4 · · · d rN + · · · +
VN
     
1 3 3 3 3 3
d rN −1 d rN fN −1 N d r1 d r2 · · · d rN −2 .
VN
   
1 3 3 N −2 1
= d r1 d r2 f12 V + N d r1 d3r3 f13 V N −2 + · · · +
3
VN V
 
1
d rN −1 d3rN fN −1 N V N −2
3
VN
 
−2 1
= V N (N − 1) d r1 d3r2 f12 .
3
2

113
    
d3r1 d3r2 f12 = d3ri d3rj fij ,

i < j
N

N! 1
= N (N − 1),
2!(N − 2)! 2

f12 , f13 , . . . , fN −1 N
  
1
2
N (N −1)

 
V −2 3
Z ≈ 1+ N (N − 1) d r1 d3r2 f12 .
2
  
I2

I2

 
3
I2 ≡ d3r2 f12
d r1
  ∞  2π  1 
3 2
= d r1 dr r f12 (r) dφ d cos θ
0 0 −1

= d3r1 η,

 ∞
η(T ) ≡ 4π dr r2 f12 (r),
0

I2 = V η.

114
 6

fij
η

N (N − 1)
Z ≈1+ η.
2V

N (N − 1) ≈ N 2 N 1

Nη
Z ≈1+N .
2V

(1 + x)n ≈ 1 + nx, x  1.

 N
Nη
Z ≈ 1+ .
2V

  N
1 3/2 N η(T )
Z≈ V (2πmkB T ) 1+ ,
N! 2V

f12 = 0 ⇒

115
 η=0

 
3/2 N η(T )
ln Z ≈ − ln N ! + N ln V + N ln(2πmkB T ) + N ln 1 +
2V

ln N ! ≈ N ln N − N
N η(T )/V  1

ln(1 + x) ≈ x, x  1.

 
N 2 η(T ) (2πmkB T )3/2
ln Z ≈ N ln V + + N ln + N.
2V N

∂ N N 2 η(T )
ln Z = −
∂V V 2V 2

∂ 3 N 2 ∂η
ln Z = N + .
∂T 2T 2V ∂T

N kB T N 2 kB T η(T )
P ≈ − .
V 2V 2

1
A(T ) = − kB T η(T ),
2

η(T ) A(T )

116
 6

3 N 2 kB T 2 ∂η
U ≈ N kB T + .
2 2V ∂T

r0

⎧
⎨ ∞, r ≤ 2r0 ;
U12 (r) =
⎩ 0, r > 2r0 ,

⎧
 
⎨ −1,
U12 (r) r ≤ 2r0 ;
f12 (r) ≡ exp − −1=
kB T ⎩ 0, r > 2r0 .

 ∞
η = 4π dr r2 f12 (r)
⎛0 ⎞
 2r0  ∞
= 4π ⎝ dr r2 f12 (r) + dr r2 f12 (r)⎠
0    2r0   
−1 0
 2r
r3  0 32πr03
= −4π  =− .
3 0 3

 
16πr03 1
A = kB T = kB T b,
3 NA

117
 NA
 
16πr03
b ≡ NA ,
3

P
V T

N kB T N 2 kB T b
P ≈ + ,
V V 2 NA

R = NA kB

N RT N 2 RT b
P ≈ + .
V V2

118
 6

P V T
N/V

N kB T N2 N3 N4
P = + A 2 + B 3 + C 4 + ··· ,
V V V V

A B C

Z=Z Z

VN
Z = (2πmkB T )3N/2 ,
N!

1  
Z ≡ d3rl exp (−βUij ) ,
VN
l i<j

1
β= ,
kB T

Uij ≡ U(ri , rj ).

P U

∂
U = kB T 2 ln Z,
∂T

119
 ∂
P = kB T ln Z.
∂V
Z

  
1 3/2 N η(T ) N
Z≈ V (2πmkB T ) 1+ ,
N! 2V

 ∞
η(T ) ≡ 4π dr r2 f12 (r),
0

r ≡ |r2 − r1 |

f12 (r) ≡ exp [−βU12 (r)] − 1.

N kB T N 2 kB T η(T )
P ≈ − ,
V 2V 2
1
A(T ) = − kB T η(T )
2

3 N 2 kB T 2 ∂η
U ≈ N kB T + .
2 2V ∂T

120
 r > 2r0 6
exp(−βU12 )

 
N 2a
P+ 2 (V − N b) = N RT.
V

V1 V2
3 × 10−2 3

5 × 10−2 3

121
 3
! 3
!
Jm m
a 10−3 mol 2 b 10−3 mol

a/Rb

122