Lecture 5 27.08.

21

Microcanonical ensemble (MCE)

Previously:
●
PEAP & MCE
●
Probabilities and microstates
●
Reservoirs

uzma, manvi, kathaa, divyansh, raunak

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 50
 Ensemble, reservoir
●
Reservoir: a large storage (of heat, particles)
●
Heat reservoir or thermal bath: A thermodynamic system with a heat capacity so
large that the temperature (intensive) of the reservoir does not change when a
reasonable amount of heat is added or extracted
●
Particle reservoir: A particle reservoir is a system in chemical equilibrium which is
so large that one can extract particles from it without changing its chemical
potential (intensive).

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 51
 Thermal Interaction
Interactions in between subsystems:
●
Thermal interaction: Two subsystem is in thermal contact, or heat exchange allowed.
●
Whole system is isolated. No exchange with surroundings.
●
Total energy of the whole system or sum of two subsystems is constant.

E = E1+E2, V = V1+V2, N = N1+N2

●
E2 = E – E1

W(E,N,V) = W1(E1,N1,V1) x W2(E2,N2,V2) = W1(E1) x W2(E-E1) P=

P(E1) = c W(E1;E0) = c W1(E1) x W2(E-E1)

E
1
=W c = ∑ W 1 ( E 1 ) W 2 ( E − E 1 )
c E 1= 0

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 52
Microcanonical ensemble (E,N,V)
E2 = E – E1

W(E,N,V) = W1(E1,N1,V1) x W2(E2,N2,V2) = W1(E1) x W2(E-E1)

P(E1) = c W(E1;E0) = c W1(E1) x W2(E-E1)

E
1
=W c = ∑ W 1 ( E 1 )W 2 ( E − E 1 )
c E 1= 0

●
As E increases, W(E) increases;
●
As W1(E1) increases and W2(E-E1) decreases. So P(E1) must display a maximum as a
func of E1.

f(E1) = ln P(E1) = ln c + ln W1(E1) + ln W2(E-E1)

At max, d ln P(E1)/dE1 = 0 = d ln W1(E1)/dE1 - d ln W2(E2)/dE2

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 53
Definition of entropy (Microcanonical)

=>

Valid in thermodynamic limit

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 54
 Microcanonical ensemble
(1) Thermal interaction: Two subsystem is in thermal contact, or heat exchange allowed.
●
Whole system is isolated. No exchange with surroundings -- Microcanonical ensemble
Total energy, volume and number of particles are fixed. (E,N,V)
●
Probability that system in given macrostate1 and 2:
W 1 ( E1 )W 2 (E−E1 )
P(E 1) = E S =k B ln W , T 1 =T 2 (equilibrium )
∑ W 1 (E1 )W 2 (E−E 1)
E1=0

(2) Thermal & mechanical interaction: Two subsystem is in thermal contact, and wall is
movable.
●
Whole system is still isolated. -- Microcanonical ensemble
W 1 (E1 ,V 1) W 2 ( E 2 ,V 2)
P( E 1 , V 1 ) = E V
, T 1=T 2 , p1= p 2
∑ ∑ W 1 (E 1 , V 1 )W 2 ( E2 , V 2 )
E 1=0 V 1= 0

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 56
 Microcanonical ensemble
(1) Thermal interaction: Two subsystem is in thermal contact, or heat exchange allowed.
●
Whole system is isolated. No exchange with surroundings -- Microcanonical ensemble
Total energy, volume and number of particles are fixed. (E,N,V)
●
Probability that system in given macrostate1 and 2:
W 1 ( E1 )W 2 (E−E1 )
P(E 1) = E S =k B ln W , T 1 =T 2 (equilibrium )
∑ W 1 (E1 )W 2 (E−E 1)
E1=0

(2) Thermal & mechanical interaction: Two subsystem is in thermal contact, and wall is
movable.
●
Whole system is still isolated. -- Microcanonical ensemble
W 1 (E1 ,V 1) W 2 ( E 2 ,V 2)
P( E 1 , V 1 ) = E V
, T 1=T 2 , p1= p 2
∑ ∑ W 1 (E 1 , V 1 )W 2 ( E2 , V 2 )
E 1=0 V 1= 0

1 ∂ k B ln W p ∂ k B ln W
●

T
= [
∂E ] N ,V T
=
∂V[ ] N

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 57
Microcanonical ensemble
●
Probability that system in given macrostate1 and 2: P = c W1 x W2
●
Definition of entropy in Statistical Mechanics: S =k B ln W
This definition is consistent with the idea that entropy is a measure of disorder.
●
The definition shows entropy is additive or extensive quantity:
Two systems W = W1 x W2 ==> S = S1 + S2

●
It is consistent with thermodynamics:

∂S ∂S 1
T dS =dE+ P dV ⇒ T
[ ]
∂E V
=1 ⇒
[ ] =
∂E V T

●
Isolated system given by N, V, E -> E + δ E , find W(E,N,V) and you get everything!

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 59
Microcanonical ensemble
●
Probability that system in given macrostate1 and 2: P = c W1 x W2
●
Definition of entropy in Statistical Mechanics: S =k B ln W
This definition is consistent with the idea that entropy is a measure of disorder.
●
The definition shows entropy is additive or extensive quantity:
Two systems W = W1 x W2 ==> S = S1 + S2

●
It is consistent with therrnodynamics:

∂S ∂S 1
T dS =dE+ P dV ⇒ T
[ ]
∂E V
=1 ⇒
[ ] =
∂E V T

●
Isolated system given by N, V, E -> E + δ E , find W(E,N,V) and you get everything!
●
An ensemble whose members are distributed among accessible microstates W in
accordance with prob. 1/W is called Microcanonical ensemble.
●
δ E: system can not be completely isolated in reality, so energy fluctuates.
●
Energy E can not be directly measured. Then how do we measure energy?

Statistical Mechanics, Sem V, 2021-2022

Dr. Poulomi Sadhukhan 61