Two Theorems: the Equipartition & the Virial

3.7.

Let

H
1
xi

xj
Z

; j 1,

d e

,6N qi , pi ; i 1,
H
xi
xj

,3N q, p

Z d e H

d d 6 N x d 3N q d 3N p

1
e H

d xi

Z
xj
1

1
Z

i j

d
j

H
xi
e

x max
j
x min
j

d xj e

xi

x j

d
x
e
i j
j
j

1
Z

H
d

d j

xi

H
i j kT
xj

d
d xi
d xj i j

xk extreme xk

xi

H
i j kT
xj

qi

pi

H
qi pi kT
qi

H
pi qi kT
pi

qi

H
qi pi 3NkT
qi
i

pi

H
pi qi 3NkT
pi
i

Equipartition Theorem
3N

i 1

H
qi
qi pi 3NkT
qi
i

3N

i 1

H Ai Pi 2 B j Q j2
i 1

H
2 A j Pj
Pj

1
f kT
2

generalized coord.
& momenta

j 1

H
2B j Q j
Qj

Q
H
H
P

Q
2H

i
j
Pi j 1 Q j
i 1

nP

H
pi qi 3NkT
pi
i

nQ

nP

Quadratic Hamiltonian :

pi

Equipartition Theorem
f = # of quadratic terms in H.

1
nP nQ kT

2
Fails if DoF frozen
due to quantum effects

Virial Theorem
Virial =

r f
i

3N kT

pj

Virial theorem

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

f n P S P S
Gaussian theorem :

Equipartition theorem :

V P

r dS

V P dV r 3 P V

1
U K 3N kT
2

PV N kT

V 2K

d-D gas with 2-body interaction potential u(r) :

V d PV

u
r

ij

r
i j
ij

d N kT
Prob.3.14

P
1
1
N kT
d N kT

u
ri j

ri j
i j

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 :

H qi , pi

1
Q1
h

dq

1 2 1
pi m 2 qi2
2m
2

i 1,

,N

1 2 1
2 2
dp
exp

2
m
2
h

Q1

Oscillators are distinguishable :

2m

kT

QN Q1

kT

2
m 2

 kT
Z QN

A kT ln Z N kT ln

kT

kT
ln

N
kT

T , V

A
P
0
V T , N
A

S

N
k
ln

Nk
T N , V
kT

kT
N k ln
1

U A T S N kT

U
CV
Nk

T N , V

H U PV N kT

H
CP
Nk

T N , P

1
U

2
N
Equipartition :
kT N kT
2

 kT
Z QN

g E

1
N

1
N

1 i
g E
d eE Z

2 i i

1 ' i
eE
d N

'

2 i

eE
E N 1
Res N

0 N 1 !

E0

contour closes on the left

E0

contour closes on the right

EN
E N 1

S k ln g E k ln

k
ln

N
ln
N

N 1 !

E
S N k ln
1

kT
S N k ln
1

1 S
Nk

T E N ,V
E
as before

Quantum Oscillators

n n
2

n 0,1,2,

1
1


Q1 exp n e 2
2
n 0

Z Q1N

1
N
2

1 e

A kT ln Z

1
1 e

2sinh
2

1
N N kT ln 1 e
2

1
1

2sinh
2

N kT ln 2sinh
2

1
N N kT ln 1 e
2

A
A

T , V N

1
kT ln 1 e
2

A
S
N k ln 1 e

T N , V

N kT ln 2sinh
2

A
P
0
V T , N

T 1 e

N k ln 1 e

1
1
1

N k ln 2sinh N
coth
2
2 T
2

U ATS

1
N
1
1

N
N coth
2
e 1
2
2

N k e
U
CV

2

T N , V
e

H U PV U

H
1

N k csch 2 CP

T N , P

1
U

2
N
Equipartition :
kT N kT
2

fails

1
1

2 e / k T 1 Schrodinger

Planck
/k T
e
1
kT

Classical

Cquantum Cclassical
Mathematica

g(E)

Z Q
N
1

1
N
2

1 e

1
N
2

N R 1! e R

R 0 N 1 ! R !

N R 1
1
d E g E e E

Z
exp N R

0
R

R0
2

g E

N R 1
1

R
2

R0

Microcanonical Version

Consider a set of N oscillators, each with eigenenergies n n

2

n 0,1,2,

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
2

R Positive integers

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

into N distinguishable oscillators (boxes).
= # of distinct ways to insert N1 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
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

E R N
2

N R

1
N
2

1
N
2

ln N R 1 ln R 1

1
N
1
k
N R
k
2

ln

ln
T

R
E1N
2
E

1
N
2
e
1
E N
2

1 S
1 S

T E N
R N

/kT

E 1
e

N 2
e

/kT
/kT

1 1

1 2 e

1
/k T

same as before

Classical Limit
E

N

Classical limit :

N 1 R !

N 1! R !

N 1 R N 2 R R 1

N 1!

R N 1

N 1!

R
S k ln k N ln R N ln N N k N ln 1
N

ER

E
S k N ln
1
N
1 S

T E N
E N kT

kN
E

2 N kT
2

equipartition

RN

N!

R N

3.9.

The Statistics of Paramagnetism

System : N localized, non-interacting, magnetic dipoles in external field H.

N

E Ei i H H
i 1

i 1

cos
i 1

( E = 0 set at H = 0 )

(Zrot cancels out )

Dipoles distinguishable

H H z

M z N cos

G T , H k T ln Z

Z QN Q1

Q1 e H cos

H cos
cos

H cos

G
ln Z
Mz

kT

H N kT

ln Q1

Classical Case (Langevin)

Dipoles free to rotate.
2

Q1 d
0

d cos e H cos

2
4
H
H
e

sinh H

H
H

( c.f. Prob 2.2 )

G N kT ln Q1 N kT ln
sinh H
H

M
z z
N

cosh H 1
ln Q1
kT

kT

H
H

T
sinh H

z coth H
L x coth x

1
x

H
L

kT

Langevin function
Mathematica

( Q , G even in H )

z L x

H
kT

L x coth x

1
x

Mz N
L x
Magnetization =
V
V

Strong H, or Low T :

Weak H, or High T :

Isothermal susceptibility :
( paramagnetic )

1
L x 1 O e 2 x
x

Mz N

V
V

x x3
L x
O x5
3 45

CuSO4 K2SO46H2O

H
3 kT

M z N 2

H
V
V 3 kT

M z
N 2
C
T lim

H 0 V H
T

H 0 V 3 kT

Curies law
C = Curies const

Quantum Case

J 2 J J 1

e
2m c

= gyromagetic ratio

3 S S 1 L L 1

2
2 J J 1

= Landes g factor

g L L g S S g B J

2 2

J = half integers, or integers

e
= (signed) Bohr magneton
2m c

2
2
J 2 g B J J 1

m g B m

H H z

g = 2 for e
( L= 0, S = )

m J , J 1,

z H g B m H

, J 1, J

 g B m H
Q1

m g B H

m J

m0

x g B J H

mx/J

m J

2J

mx/J

2 J 1 x / J
1

e
e x
1 ex / J

e 2 J 1 x / 2 J e 2 J 1 x / 2 J

e x / 2 J e x / 2 J

e x

e 2 J 1 x / 2 J e 2 J 1 x / 2 J
e 2 J 1 x / 2 J e 2 J 1 x / 2 J

1

sinh x 1
2J

x
sinh

2J

1

G N kT ln sinh x 1
2J

ln
sinh

2J
( Q , G even in e & H )


1

G N kT ln sinh x 1
2J

x
ln sinh

2J

G
1
Mz
N g J B 1

T
2 J

x g B J H

kT

x
g B J
H

1 1

x
coth
coth x 1

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
2 J 2 J
2
J
2
J

Mathematica

Mz
g B J BJ x
N

Limiting Cases
1
1 1

x
BJ x 1
coth
x
1

coth

2 J 2 J
2J

2J

coth y

e e
e y e y
y

2 y

1 e
1 e 2 y

1 2e 2 y

1 y
y3

y
y0

2
2
BJ x 1
1 1 1
1
x
1

x
1

3 2 J 2 J 3
J

g B J

z g J B BJ x
2
1

H
B
J J 1 g 2

B
3
kT
3 kT

N 2
Curies const = CJ
V 3k

x g B J H

x
x0

gJ

B H

gJ

B H

kT
kT

2 g 2 B2 J J 1

Dependence on J
x g B J H

1
1 1

x
BJ x 1
coth
x
1

coth

2 J 2 J
2
J
2J

2 g 2 B2 J J 1

J ( with g 0 so that is finite ) :

x ,

BJ x L x 1

~ classical case

2 3 B2

J = 1/2 ( most quantum case ) :

coth 2 x 1
coth x
B1/2 x 2coth 2 x coth x
coth x

g =2

z g J B BJ x

C1/2

tanh x

B
B tanh x
B B H

kT

N 2
N B2
CJ

V 3k
V k

J 1/2

B H

kT
B H
0
kT

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

J= ,g=2

Q1 e m e e

1
2

m g B m H
Z QN e e

G kT ln Z N kT ln e

dG SdT M d H d N

B H
2cosh

M is extensive; H, intensive.

tanh
M
B

kT
H T , N

kT

M H U S, H , N
U here is the enthalpy.

N kT ln 2cosh
G T , H , N
kT

N
k
ln
2cosh

N
tanh

kT
T
kT
T H , N

U G T S N tanh

U
2
2
C

N
sech

T
kT
kT

H , N
Note: everything except M is even in H.

 2N

Ordered
(Saturation)

Disordered
(Random)

Mathematica

CN

2
kT

sech

kT

kT 2 e / k T e / k T 2

2
e / k T
N 2
kT e / k T 12

2 energy gap

Peak near / kT ~ 1
( Schottky anomaly )

Absolute T
Two equivalent ways to define the absolute temperature scale :

1.Ideal gas equation.

T 0 P0

PV n R T

Dynamically unstable.
2.Efficiency of a Carnot cycle.

e 1

TC
TH

T 0 e 1
Violation of the Kelvin &
Clausius versions of the 2nd law.

Definition of the temperature of a system : T U

U is any thermodynamic potential

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.

T < 0 possible if E is bounded.

e.g.,

U N tanh

kT

Usually T > 0 implies U < 0.

But T < 0 is also allowable if U > 0.

B H

( U is even in H )

U = 0 set at H = 0

U N tanh

ln 2cosh

tanh

Nk
kT
kT

kT

cosh x

Also

kT

2 N

N U N U

1 1 x
tanh x ln
2 1 x
1

1 tanh 2 x

S ln

cosh

S
ln

Nk

kT

kT

B H
1
U
1

N U N U

U
U

tanh 1
N
N

tanh 1

U
N

2 N

N U N U

1 N U
ln
2 N U

U
N U

ln
2N N U


S
ln

Nk

2 N

N U N U

U
N U

ln
2N N U

kT

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

2N
2N
2N
2N

Mathematica

1 N U
ln
2 N U

U N tanh

Heat Flow

B H

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

T:

0 0+
Mathematica

small to large

kT

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 = 105 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

Z QN Q1N e n
n

1 2 2

n 1 n 2 n

___

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

g
n

1 2 ___2
Z g 1
2

1 2 ___2
ln Z N ln g ln 1
2

1
1

ln 1 x x x 2 x 3
2
3

1 2 ___2 1
1 2 ___2
N ln g
2
2

1 2 ___2 2
N ln g
2

n 1

___________

1 2 ___2 2
1 2
2
ln Z N ln g N ln g
2
2

___________

1
2
A N , ln Z ln g N N

2 A
S

N
T N

___________
N
1
2
k 2 ln g N
2

1 2 ___2 2
S N k ln g
2

max S S

___________
2

U A T S N N

N k ln g

U is larger for smaller

Energy flows from small to large

negative T is hotter than T = +

2
2 U
2
C N,

N
k

N
T N

___________