Statistical Thermodynamics

Thermodynamics
(Bulk Properties)

Statistical
Thermodynamics
Partition
function

Quantum Mechanics
Molecular structure,
Spectroscopy
(individual properties)
Wave
function

Goal of Statistical Mechanics: describe macroscopic bulk Thermodynamic

properties in terms of microscopic atomic and molecular properties.
Theories of Reaction Rates
bridge between microscopic properties and macroscopic reaction rate:result of many
microscopic collisions
Collision Theory based on kinetic theory fraction of collisions that are effective in
causing reaction
Transition-State Theory based on stat. mech. probability that a special state (transition
state) is occupied)
reaction dynamics, potential energy surfaces

Calculation of Properties
Statistical Mechanics describes macroscopic bulk Thermodynamic properties in terms of microscopic atomic and
molecular properties. These microscopic properties are generally measured by spectroscopy.

Macroscopic: U, H, A, G, S, , p, V, T, CV, Cp

Microscopic: N particle monatomic gas

Calculation of macroscopic properties

How do we calculate a macroscopic property, which is constant in time, from
a microscopic property that fluctuates in time?
Example: Pressure, which is a macroscopic property that arises from the microscopic
impulses of each molecule impacting the vessel's walls. The positions and velocities of
each molecule change on 10-1010-13s time scale (the duration of a collision)!

Alternative: Ensemble Average !

ENSEMBLES: An ensemble is a collection of all microstates of a system, consistent with the

constraints with which we characterize a system macroscopically.

Distribution of molecular states

Statistical Ensembles
ENSEMBLES: An ensemble is a collection of all
microstates of a system, consistent with the
constraints with which we characterize a system
macroscopically.

For example, a collection of all possible states of

the 1023 molecules of gas in the container of volume
V temperature T is a statistical mechanical
ensemble.
CANONICAL ENSEMBLE: CONSTANT N,V,T
MICROCANONICAL ENSEMBLE: CONSTANT U,V,N
GRAND CANONICAL ENSEMBLE: CONSTANT ,V,T

Distribution of molecular states

Let, N no. of particles is distributed in various energy lavels.
No. of molecules: n0 n1 n2 n3 .... In Energy levels: E0 E1 E2 E3.
Then, instantaneous configuration: {n0, n1, n2, n3, ...}
No. of ways it happens,
Weight of the
Configuration (W):

N!
N!

n0 !n1 !n2 ! ni!

i

Examples:
For {5,0,0}: W = 1
For {3,2,0}: W = 10
(shown in fig.)

Most Probable configuration has the highest W.

Specification of state of the system

Describing the outcome of each experiment

P
i

W
i
W j
j

10
100

For system containing a large no. of units

(macroscopic system) , one configuration will
have vastly more associated permutations than
any other configuration. This configuration will
be the only one that is observed to an
appreciable extent.

tossing of coin

The most probable / dominating distribution

Most probable distribution
have largest W
For Constant E and N:

E ni Ei , N ni
i

Boltzmann Distribution:

E /kT
Pi e i
Pi: fraction of molecule in state i

W = 181180
858
= N! / (N1! N2! )

78

12870

Probability of microstates

Probability of microstates
The probability of each microstate in the canonical ensemble (constant N,V, T )
is proportional to the exponential of the energy divided by the temperature.

In order to find the absolute probability of each microstate, we need to make

sure that the sum of all the probabilities is one. The normalization constant
for this is called the "canonical partition function," Q.

The summation over microstates is performed over all energies and

particle positions.

Partition function
Once the partition function is defined, the probability of each microstate can
now be written explicitly:

Therefore, in the canonical ensemble, a general property F is given by

The ensemble average

Average of any property A : A A P A
i i
i
E
i
E / kT
e
Pi
; Z e i
i
Z
1 / kT ; Z : the canonical partition function

Clearly,i Pi 1
At T = 0, Ei /kT = => Z = 1
At very large T, Ei /kT = 0 => Z 1+ 1+. =
At intermediate T (let kT >> E1, E2) => Z ~ 1+ 1+ 1 +0 +. = 3
Z gives the number of thermally accessible states at the temperature of
interest.

The Partition Function, examples

Z

E / kT
E / kT
E / kT
E / kT
e i
e 0
e 1
e 2

Vibrational:
Zv = 1 / [1 exp(- h/kT)]

P
i

E
i
e
Z

The Partition Function, examples

Z

E / kT
E / kT
E / kT
E / kT
e i
e 0
e 1
e 2

Vibrational:
Zv = 1 / [1 exp(- h/kT)]
Translational:
ZT = (2mkT)3/2V / h3
Rotational:
ZR = kT / hB, : symmetry no.
= 1 for unsymm. Lin. Rotor (HCl)
= 2 for symm. Lin. Rotor (H2, CO2)

Electronic:
ZE is not available in closed form
Molecular:
Z = ZT ZR ZV ZE ZS

Thermodynamic properties
Ei e

U pi Ei i
Z
i
e Ei
Ei Z

i
V , N B
V , N V , N B i

Internal Energy:

Since, Ei
i

E
i
e

Ei

ln Z
1 Z
2 ln Z
U

kT

V , N
T V , N
Z V , N

B
B
B
Pressure:

1 Z
P

Z V T , N

P pi Pi
i
1 ln Z

V T , N

dU (Ei / V ) N B dV
dwrev Pi dV (reversible adiabatic)
Pi (Ei / V ) N B
B

Thermodynamic properties
Z e Ei
i

1 ln Z
P

V T , N
B
ln Z
2
kT

T V , N B
S U / T k ln Z

A kT ln Z
ln Z
B RT

N B T ,V , NC B