3.7.

Two Theorems: the “Equipartition” & the “Virial”

Let x j ; j  1, ,6 N   q , p ; i  1,
i i ,3N   q, p

H 1 H d  d 6 N x  d 3 N q d 3 N p
xi   d e
 H
xi Z   d e  H
xj Z xj

1  e  H

Z  d xi  x j
  H  xi  d
1 x max
d j     d xi
 d    d xj e  H

j
e xi 
Z j
 x min
j  x j  d xj i  j

1  
    
d  d x e  H
 i j  H xk  extreme xk 
Z j j

1 H
 i j    H
d e   i j kT
Z  xi
xj
 H
xi   i j kT
xj

H H
 qi
 qi
  qi pi  kT 
i
qi
 qi
  qi pi  3NkT
i

H H
 pi qi  kT
pi
 pi 
i
pi
 pi
  pi qi  3NkT
i
 Equipartition Theorem
3N
H 3N
H

i 1
qi
 qi
  qi pi  3NkT
i

i 1
pi
 pi
  pi qi  3NkT
i

nP nQ

Quadratic Hamiltonian : H   Ai Pi 2   B j Q j2 generalized coord.

i 1 j 1 & momenta

 H H
 2 Aj Pj  2B j Q j
 Pj Qj

H H
nP n

 nP  nQ  kT
Q
1
 
i 1
Pi   Q
 Pi j  1 Q j
j  2H  H 
2

1 Fails if DoF frozen

H  f kT Equipartition Theorem
2 due to quantum effects
f = # of quadratic terms in H.
 Virial Theorem

Virial = V  r  f
i
i i  q j pj  3N kT Virial theorem
j

Ideal gas: f comes from collision at walls ( surface S ) :

f  n P  S   P S  V  P  S
r dS

Gaussian theorem : V   P  dV   r  3 P V  PV  N kT

1
Equipartition theorem : U  K  3N kT  V  2K
2
d-D gas with 2-body interaction potential u(r) :

 u  P 1 u
V  d PV   ri j      d N kT   1  ri j
  r N kT d N kT  ri j
i j  ij  i j

Prob.3.14 Virial equation of state

 3.8. A System of Harmonic Oscillators
See § 7.3-4 for applications to photons & phonons.

System of N identical oscillators :

1 2 1
H  qi , pi   pi  m  2 qi2 i  1, ,N
2m 2
 
1   1 2 1 2 2  1 2m 2
Q1      dq  dp exp   p  m  q  
h    2 m 2  h  m 2 

1 kT
Q1     
 

N
 kT 
QN     Q1    
N
Oscillators are distinguishable :  
  
   
N
 kT 
Z  QN     A  kT ln Z  N kT ln  
    kT 

 A    
    kT ln  kT 
  N T , V  

 A 
P    0
  V T , N

 A      kT  
S      N k ln    Nk  N k ln    1
 T  N , V  kT     

 U 
U  A  T S  N kT CV     Nk
 T  N , V

 H 
H  U  PV  N kT CP     Nk
 T  N , P
1 
Equipartition : U  2 N  kT   N kT
2 
 N
 kT  1   i
Z  QN    g E   d eE Z   0
   2 i    i 

1 1  '  i eE
g E 
2 i  '  i 
d N
  
N

  eE  E N 1
1  Res  N   E0 contour closes on the left
      0  N  1 !
 
N
 contour closes on the right
 0 E0

 E N 1  
  EN  

S  k ln g  E   k ln    k  ln     N ln N  N  
          
N

N
 N 1 !   


  E   1  S  Nk
S  N k  ln    1   
 N   T   E  N , V E

  kT  
 S  N k  ln    1 as before
   
 Quantum Oscillators

 n   n   
1 n  0,1,2,
 2 

  1 
Q1      exp     n      e 2
1
   1 1

n 0   2  1  e  
1 
2sinh    
2 
1
 N  N
e 2
 1 
Z  Q1N   2sinh    
1  e 
  N
 2 

 1 
 N   N kT ln 1  e   
1
A  kT ln Z 
 N kT ln 2sinh     
2  2 
 N   N kT ln 1  e     1 
1 
A  N kT ln 2sinh     
2  2 

 A   A 
  kT ln 1  e   
A 1
     
P    0
  N T , V N 2   V T , N

 e 
  e  

 A 
S      N k ln 1  e   
 N  N k   ln 1  e   

 T  N , V T 1  e  

 
 1 

 1  1  1 
  N k ln 2sinh       N coth    
 2  2 T 2 

1 N  1 1 
U  ATS  N     N  coth     H  U  PV  U
2 e 1 2 2 

N k     e 
2
 U  1  1 
2
 H 
CV      N k     csch 2      CP   
 T  N , V  
  2
e  1 2  2   T  N , P
1 
Equipartition : U  2 N  kT   N kT fails
2 
 

1 1

 2 e  / k T  1 Schrodinger

  1
  /k T
Planck
  e 1
 kT
 Classical
 

Cquantum  Cclassical

Mathematica
 g(E)

1
 N  R  1! e R 
 N  1 
 N 

2
e 
Z Q 
N
e 2

1  e  R  0  N  1 ! R !
1
  N


 N  R  1  1   
Z    exp     N  R     0 d E g  E  e  E

R0 R   2  

 N  R  1

 1  
 g E   
R0
  

E  
2
N  R  
 
R 
 Microcanonical Version
 1  n  0,1,2,
Consider a set of N oscillators, each with eigenenergies  n   n   
 2 
Find the number  of distinct ways to distribute an energy E among them.

Each oscillator must have at least the zero-point energy  disposable energy is

1
E  E  N R  R  Positive integers
2

  = # of distinct ways to put R indistinguishable quanta (objects)

into N distinguishable oscillators (boxes).
= # of distinct ways to insert N1 partitions into a line of R object.

 
 N  1  R !
 N  1! R !
 N = 3, R = 5
Number of Ways to Put R Quanta
into N States

# of distinct ways to put R indistinguishable quanta (objects)

into N distinguishable oscillators (boxes).


 N  1  R !
 N  1! R !

Mathematica

 N  1  R !
 N  1! R ! S

S
  ln    N  R  ln  N  R    N  R    N ln N  N  R ln R  R 
k
  N  R  ln  N  R   N ln N  R ln R

 1  1  S  1  S  k
E  R N        ln  N  R   1  ln R  1
 2  T   E N    R  N 
E 1
R  N 1
N  E
 2 1 k NR k
  ln  ln 2
E 1 T  R  E1N 
NR  N
 2 2
1
E N  /kT
2 /kT E 1 e 1  1 1 
 e       /k T  
1
E N  N 2 e /kT
1  2 e 1
2
same as before
 Classical Limit
 1 
E  R  N 
Classical limit :       2 
   R  N
N N


 N  1  R !

 N  1  R  N  2  R   R  1

R N 1 RN

 N  1! R !  N  1!  N  1 ! N!

S  k ln   k  N ln R  N ln N  N   k N  ln  1

R
 N 
 E 
ER   S  k N  ln  1
 N  
1  S  kN
  
T   E N E

1 
E  N kT   2 N  kT  equipartition
2 
 3.9. The Statistics of Paramagnetism
System : N localized, non-interacting, magnetic dipoles in external field H.

N N N
E   Ei    μi  H    H  cos i ( E = 0 set at H = 0 )
i 1 i 1 i 1

(Zrot cancels out )

Dipoles distinguishable  Z  QN     Q1    

N
Q1      e   H cos


 cos  e   H cos 

H  H zˆ  M z  N  cos  N 



e H cos 

 G    ln Z    ln Q1 
G T , H   k T ln Z  Mz     kT    N kT  
  H T   H T   H T
 Classical Case (Langevin)
Dipoles free to rotate.

2 4
 
2
Q1      d  d cos e   H cos sinh    H 
1
 H   H
 e  e 
0 1  H  H
( c.f. Prob 2.2 )
 4 
G   N kT ln Q1   N kT ln  sinh    H   ( Q , G even in H )
 H 

M   ln Q1     cosh    H  1 
z  z  kT    kT   
N   H T  sinh    H  H

1  H 
 z   coth    H    L 
H  kT 
1
L  x   coth  x   Langevin function
x
Mathematica
 H 1
z   L  x  x L  x   coth  x  
kT x

Mz N CuSO4 K2SO46H2O
 Magnetization =   L  x
V V

 O  e 2 x 
1
Strong H, or Low T : x 1 L  x  1 
x
Mz N
z    
V V

x x3
Weak H, or High T : x 1 L  x     O  x5 
3 45
H M z N 2
z    H
3 kT V V 3 kT
 M z  N 2 C
Isothermal susceptibility : T  lim     Curie’s law
H 0 V H
( paramagnetic )   H  0 V 3 kT T
C = Curie’s const
 Quantum Case

μ J J 2  J  J  1 J = half integers, or integers

e
 g = gyromagetic ratio
2m c

3 S  S  1  L  L  1
g  = Lande’s g factor g = 2 for e
2 2 J  J  1 ( L= 0, S = ½ )
e
μ  g L L  g S S  g B J B  = (signed) Bohr magneton
2m c

2   2 J 2  g B J  J  1
2 2 2

z   m  g B m m   J ,  J  1, , J  1, J

H  H zˆ      z H   g B m H
   g B m H

J J
Q1     e
m  J
m  g B H
 e
m  J
mx/J
x   g B J H

 
 2 J 1 x / J
 e 
 2 J 1 x / 2 J 2 J 1 x / 2 J

2J
e x
e mx/J
 e x
1 e x e
 e 2 J 1 x / 2 J
1  ex / J e  
 2 J 1 x / 2 J
m0 e

  1 
sinh  x  1  
e  2 J 1 x / 2 J  e 2 J 1 x / 2 J   2J 
 
e x / 2 J  e x / 2 J  x 
sinh  
 2J 

   1   x 
G   N kT ln sinh  x 1    ln sinh  
   2J   2J  

( Q , G even in e & H )
 x   g B J H
   1   x 
G   N kT ln sinh  x 1    ln sinh    x
   2J   2J   kT  g B J
H

 G   1    1  1  x 
Mz     N g J  
B  1   coth  x 1    coth  
  H T  2 J    2 J  2 J  2 J 
( M is even in e & // H )
 1    1  1  x 
BJ  x    1   coth  x  1    coth   = Brillouin function
 2J    2 J  2 J  2 J 
Mz
Mathematica z   g  B J BJ  x 
N
 Limiting Cases
 1    1  1  x 
BJ  x    1   coth  x  1    coth   x   g B J H
 2J    2 J  2 J  2J 

y 2 y
 1  2e 2 y y
e e
y
1 e 
coth y    1 y
e y  e y 1  e 2 y  y3 y0

 1 x

 BJ  x    1  1   1   1 
2 2
1
  
 3  2 J   2 J   3 
x 1 x 1   x0
   J 

 B H
 g B J gJ 
z  g J B BJ  x   
kT
 1 J  J  1 g 2  B H   H B H
2
gJ 0
 3 B
kT 3 kT kT

N 2
 Curie’s const = C J   2  g 2 B2 J  J  1
V 3k
 Dependence on J
 1    1  1  x  x   g B J H
BJ  x    1   coth   2J
x 1    coth  
 2J     2 J  2J 
 2  g 2 B2 J  J  1
J   ( with g  0 so that  is finite ) :

 x  , BJ  x   L  x   1 J ~ classical case

J = 1/2 ( “most” quantum case ) :  2  3 B2

coth 2 x  1
B1/2  x   2coth  2 x   coth x   coth x  tanh x
coth x
 B H
  B kT

g =2  z  g J B BJ  x   B tanh x  
 B B H B H
0
 kT kT
N  B2 N 2
 C1/2    CJ J  1/2
V k V 3k
Gd2(SO4)3 · 8H2O
J = 7/2, g = 2

FeNH4(SO4)2 · 12H2O,
J = 5/2, g = 2

KCr(SO4)2
J = 3/2, g = 2
 3.10. Thermodynamics of Magnetic Systems: Negative T
1
J=½ ,g=2  m  m   g B m H     B H
2
Q1      e   m  e    e     Z  QN      e    e   
N
  2 cosh  
N

  
G  kT ln Z   N kT ln  e 
e  
   N kT ln  2cosh   G T , H , N 
 kT 
 d G   SdT  M d H   d N M is extensive; H, intensive.

 G      
S     N k ln  2cosh   N tanh
  T H , N  kT  T kT

 G 
M     N  B tanh
  H T , N kT


U  G  T S   N  tanh  U  2 2 
kT C    N sech
 T  H , N kT 2 kT
  M H  U  S, H , N 
U here is the “enthalpy”. Note: everything except M is even in H.
   2N

Ordered Disordered
(Saturation) (Random)

Mathematica
 2  2 4 2 e / k T
CN sech 2
N N 2
kT 2
kT kT 2  e  / k T  e / k T 2 kT  e  / k T  12

  2  energy gap

Peak near  / kT ~ 1
( Schottky anomaly )
 Absolute T

Two equivalent ways to define the absolute temperature scale :

1. Ideal gas equation. PV  n R T T 0  P0

Dynamically unstable.
TC
2. Efficiency of a Carnot cycle. e  1 T  0  e 1
TH
Violation of the Kelvin &
Clausius versions of the 2nd law.

Definition of the temperature of a system : T   U U is any thermodynamic potential

S with S as an independent variable.

T 0  S  as U 
Impossible if Er is unbounded above.
 T<0

Z   e  E  E  0 Z finite  T  0 if E is unbounded.
E

 T < 0 possible if E is bounded.


e.g., U   N  tanh   B H ( U is even in H )
kT

Usually T > 0 implies U < 0.

U = 0 set at H = 0
But T < 0 is also allowable if U > 0.
 
S      U   N  tanh
 ln  2cosh   tanh kT
Nk  kT  kT kT
  B H
1  1 N
cosh x   cosh  
1  tanh 2 x kT  U 
2
 N   U  N   U 
1  
 N  

 2 N  U U
 S  ln   tanh 1

  N  U  N   U   N

N

1 1 x  U 1 N  U
1
tanh x  ln    tanh 1  ln
2 1 x kT N 2 N U

S  2 N  U N  U
Also  ln   ln
Nk 
  N   U  N   U   2N  N  U

  1 N  U
  U  ln
S 2 N N  U kT 2 N U
 ln   ln
Nk 
  N   U  N   U   2N  N  U


1 U  1 U 
 ln  2 N    1   ln  N   U   1   ln  N   U 
2  N  2  N 

N  U  N  U  N  U  N  U 
 ln   ln  
2 N  2 N  2 N  2N  

Mathematica
 
U   N  tanh
kT
Heat Flow
  B H

Flow of U (as Q) : High to low.

T: 0      0+ :   
small to large
Mathematica
 Experimental Realization
Let t1 = relaxation time of spin-spin interaction.
t2 = relaxation time of spin-lattice interaction.

Consider the case t1 << t2 , e.g., LiF with t1 = 105 s, t2 = 5 min.

System is 1st saturated by a strong H ( US =  HM < 0 ). H is then reversed.

Lattice sub-system has unbounded E spectrum so its T > 0 always.
For t1 < t < t2 , spin subsystem in equilibrium; M unchanged  US = HM > 0  TS < 0.
For t2 < t , spin & lattice are in equilibrium  T > 0 & U < 0 for both.

T  300K

T  350K
NMR

T  (   + ) K
T < 0 requires E bounded above:
Usually, K makes E unbounded  T < 0 unusual

T > 0 requires E bounded below :

Uncertainty principle makes E bounded below  T > 0 normally
 T >> max
kT  max   n 1 n
N N
    
Z  QN     Q1N    e   n 
1 2 2

 n 


n  1   n 
2
 n  

g ___

Let g = # of possible orientations (w.r.t. H ) of each spin  n n


n
 
 g  

n 1


N
  1 2 ___2  
 Z   g 1         
  2  

  1 2 ___2   1 1 
ln Z  N ln g  ln 1         ln 1  x     x  x 2  x 3  
  2   2 3 
  1 2 ___2  1  1 2 ___2 
2

 N ln g                  
  2  2 2  
 1 2  ___2 2  
 N ln g            
 2   
  1 2  ___2 2   1 2 2
___________
ln Z  N ln g            N ln g            0
 2    2 
___________
1 N 1
A  N ,     ln Z   ln g  N   N     
2

  2

 A   2 A 
 N 1 2
___________

 S     k    k  2  2 ln g  N     
  T N    N   2 

 1 2  ___2 2 
S  N k ln g        max S  S  0
 N k ln g
 2  
___________

U  A  T S  N   N      U is larger for smaller 

2

 Energy flows from small  to large 

 negative T is hotter than T = +

 U   2  U 
___________

C N,               0
2 2
  k  N k
  T N    N