Few concepts of

statistical mechanics
Outlines
• Degrees of Freedom
• Position Space
• Momentum Space
• Phase Space
μ-space (Molecular Space)
Γ-space (Gamma Space)

• Phase Points and Division of Phase Space into Cells

• Calculation of Phase Space Area
• Macrostates and Microstates

Introduction 2
Degrees of Freedom
The total number of independent variables required to describe completely the state of
motion of a body.
 An ant moving in straight line has one degree of freedom (x). If it moves on a plane,
then it has two degrees of freedom (x, y).
 A flying insect (mosquito) in air has three degrees of freedom (x, y, z).
 A rigid body that not only moves but also rotates has 6 degrees of freedom ( 3 for
translational motion & 3 for rotational motion).

Position Space
Consider a system of N particles in a volume V. If the system is static, all the particles will
remain fixed at various points in space. To completely specify the position of any particle
in the 3D space, we must know the values of its three Cartesian coordinates x, y, z.

Introduction 3
The three dimensional space in which the location of a particle is completely specified by
the three position coordinates is known as position space.
A small volume element in position space is denoted by 𝑑𝑉 and is given by
𝑑𝑉 = 𝑑𝑥𝑑𝑦𝑑𝑧
Momentum Space
If the system is dynamic, the particles of the system will move with various velocities and
hence they will posses momenta. A complete specification of such a system cannot be
described in terms of the position coordinates only. We must need the help of velocity
components 𝑣𝑥 , 𝑣𝑦 , 𝑣𝑧 which are related to the momentum components by
𝑝𝑥 = 𝑚𝑣𝑥 , 𝑝𝑦 = 𝑚𝑣𝑦 , 𝑝𝑧 = 𝑚𝑣𝑧
The three dimensional space in which the momentum of a particle is completely specified
by the three mutually perpendicular momentum coordinates 𝑝𝑥 , 𝑝𝑦 , 𝑝𝑧 is known as
momentum space.
A small volume element in momentum space 𝑑𝑉is given by, 𝑑𝑉 = 𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧 .

Introduction 4
Phase Space
A combination of position space and momentum space is known as phase space. It is a six
dimensional space. The specification of the position of a particle in phase space needs six
coordinates: 𝑥, 𝑦, 𝑧, 𝑝𝑥 , 𝑝𝑦 , 𝑝𝑧 . The coordinates are mutually perpendicular to each other.
A small volume element in phase space 𝑑𝑉is given by,
𝑑𝑉 = 𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧
i. μ-space (Molecular Space)
A 6 dimensional space which describes the motion of each individual particles of a large
system is known as μ-space or molecular space.
If we consider a system of N molecules, the motion of each molecules of the system will
be described by using six coordinates (3 position & 3 momentum) in this space.
ii. Γ-space (Gamma Space)
It is a 6N dimensional phase space representation in which a single point represents the
state of entire N-particle system.

Introduction 5
Phase Space Representation

Introduction 6
Summary
1) Position Space – f dimensional

2) Momentum Space – f dimensional

3) μ-space (Molecular Space) – 2f dimensional (f for position + f for momentum )

4) Γ-space (Gamma Space) – 2fN dimensional

where f represents the number of coordinates required to completely describe a system.

Introduction 7
Phase Points
In a phase space the state of an individual system or molecules may be represented by a
point which is known as the phase point or representative point. The phase space may be
divided into cells 1, 2, 3,.., i. A phase point for any system or molecule may reside in one
of these cells.
Phase Cells
A phase space may be divided into a number of six dimensional cells whose sides are
𝑑𝑥, 𝑑𝑦, 𝑑𝑧, 𝑑𝑝𝑥 , 𝑑𝑝𝑦 , 𝑑𝑝𝑧 . These cells are called phase cells. The volume of such a cell is
𝑑τ = 𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧
According to uncertainty principle, 𝑑𝑥𝑑𝑝𝑥 ≥ ℎ, 𝑑𝑦𝑑𝑝𝑦 ≥ ℎ and 𝑑𝑧𝑑𝑝𝑧 ≥ ℎ.
∴ 𝑑τ ≥ ℎ3
The minimum volume of a phase cell is of the order of ℎ3 .
So the particle in phase space cannot be considered exactly located at points
𝒙, 𝒚, 𝒛, 𝒑𝒙 , 𝒑𝒚 , 𝒑𝒛 but can only be found somewhere within a phase cell concentrated at
that point.

Introduction 8
Calculation of Phase Space Area/Number of Phase Cells
Case – I: Harmonic Oscillator

Case – II: Free Particle

Introduction 9
Case – I: Harmonic Oscillator
We consider a linear simple harmonic oscillator of mass m which is oscillating freely with
frequency υ.
i. We will calculate the number of phase cells in the energy range 0 to E.
ii. The phase space area of the harmonic oscillator.
Since it is a one dimensional system, the phase space diagram contains one position
coordinate x and one momentum coordinate p. So, it is a p, x plane.
At any instant, the total energy E of the oscillator is given by,
𝐸 = 𝑃𝐸 + 𝐾𝐸
1 2 1 2
= 2
𝑘𝑥 + 2
𝑚𝑣
2 𝑝2
∴ 2𝐸 = 𝑘𝑥 + 𝑚
…………(1)
Dividing eq. (1) by 2E we get,

Introduction 10
Case – I: Harmonic Oscillator
𝑘𝑥 2 𝑝2
+ =1
2𝐸 2𝑚𝐸

𝑥2 𝑝2 2𝑚𝐸
or, 2𝐸 + 2𝑚𝐸 =1
𝑘 2𝐸/𝑘

𝑥2 𝑝2
or, + = 1,………….…(2)
𝑎2 𝑏2
2𝐸
where 𝑎 = and 𝑏 = 2𝑚𝐸. Fig. 02: Phase space diagram of a 1D HO
𝑘

Equation (2) represents an ellipse in the x, p phase diagram and the points of E lies on this
2𝐸
ellipse, having major and minor axes as and 2𝑚𝐸 respectively.
𝑘

Introduction 11
(i) Phase Space Area
The area of the ellipse in phase space is given by,
𝐴 = 𝜋𝑎𝑏
2𝐸
=𝜋 × × 2𝑚𝐸
𝑘

𝑚
∴ 𝐴 = 2𝜋𝐸 ,…………(3)
𝑘

Equation (3) represents the classical phase space area available to the oscillator having
energy between 0 and E.
Now, the phase space available to the oscillator having energy between E and 𝐸 + 𝑑𝐸 is
given by,
𝑚
δ𝐴 = 2𝜋 𝑘
𝛿𝐸,…………(4)

Introduction 12
(ii) Number of Phase Cells
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑝ℎ𝑎𝑠𝑒 𝑠𝑝𝑎𝑐𝑒
𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑃ℎ𝑎𝑠𝑒 𝐶𝑒𝑙𝑙𝑠 =
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑜𝑛𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝ℎ𝑎𝑠𝑒 𝑐𝑒𝑙𝑙𝑠
𝑚
Area of phase space = 𝐴 = 2𝜋𝐸
𝑘

We know that the frequency of the harmonic oscillator is given by,

1 𝑘
𝜗=
2𝜋 𝑚
𝑚 1
or, = 2𝜋𝜗
𝑘

1 𝐸
⸫ Area of phase space = 𝐴 = 2𝜋𝐸 × =
2𝜋𝜗 𝜗

Introduction 13
(ii) Number of Phase Cells

Now, Area of one phase cell = 𝛿𝑥 𝛿𝑝 = h

𝐸
𝜗 𝐸
⸫ 𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑃ℎ𝑎𝑠𝑒 𝐶𝑒𝑙𝑙𝑠 = =
ℎ ℎ𝜗

Introduction 14
Case – II: Free Particle
We consider a particle of mass m which is moving freely in a phase space of volume
𝑉𝑝ℎ𝑎𝑠𝑒 .
i. We will calculate the number of phase cells in the energy range from 0 to E.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝ℎ𝑎𝑠𝑒 𝑠𝑝𝑎𝑐𝑒

𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑃ℎ𝑎𝑠𝑒 𝐶𝑒𝑙𝑙𝑠 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑛𝑒 𝑝ℎ𝑎𝑠𝑒 𝑐𝑒𝑙𝑙
The volume of each phase cell is,
𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧 = ℎ3
Now, the total volume of phase space,
𝑉𝑝ℎ𝑎𝑠𝑒 = ම 𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧

Here, ‫𝑉 = 𝑧𝑑𝑦𝑑𝑥𝑑 ׮‬, the total physical volume.

Introduction 15
Case – II: Free Particle
∴ 𝑉𝑝ℎ𝑎𝑠𝑒 = 𝑉 ‫𝑧𝑝𝑑 𝑦𝑝𝑑 𝑥𝑝𝑑 ׮‬
Since the volume of momentum space is equal to the volume of sphere of radius p, we get
4 3
ම 𝑑𝑝𝑥 𝑑𝑝𝑦 𝑑𝑝𝑧 = 𝜋𝑝
3
4
= 𝜋( 2𝑚𝐸)3
3

4 3Τ
= 3
𝜋(2𝑚𝐸) 2

4𝜋𝑉 3ൗ
∴ 𝑉𝑝ℎ𝑎𝑠𝑒 = (2𝑚𝐸) 2
3
4𝜋𝑉 3Τ
Hence, the total number of phase cells in the phase space = (2𝑚𝐸) 2
3ℎ3

Introduction 16
Macrostates
and
Microstates

Introduction 17
(i) Macrostates
The macrostate of an assembly of systems or molecules may be defined by the
specification of phase points in each cell i.e., by specifying the numbers only and
overlooking the identities of the systems or molecules.

(ii) Microstates
The microstate of an assembly of systems or molecules may be defined by the
specification of the individual position of phase points for each system or molecules of the
assembly.
Actually, a large number of microstates constitutes a macrostate. In other words, a
macrostate consists of a number of microstates.

Example: We consider a phase space which is divided into four cells: cell 1, cell 2, cell 3,
cell 4. We also consider four phase points, a, b, c, and d.

Introduction 18
Now, the macrostates corresponding to the phase points, 𝑛1 = 4, 𝑛2 = 3, 𝑛3 = 2, and
𝑛4 = 1 can be shown as follows:

𝑛1 = 4 𝑛2 = 3 𝑛3 = 2 𝑛4 = 1

𝒂𝒃𝒄𝒅 𝒂𝒃𝒄 𝒂𝒃 𝒂

Cell 1 Cell 2 Cell 3 Cell 4

Each of these macrostates contains a number of microstates. Now, the microstates

corresponding to the macrostate 𝑛3 = 2 and 𝑛4 = 1.

𝒏𝟑 = 𝟐 Cell 3 𝒂𝒃 𝒂𝒄 𝒂𝒅 𝒃𝒄 𝒃𝒅 𝒃𝒂 𝒄𝒅 𝒄𝒂 𝒄𝒃 𝒅𝒂 𝒅𝒃 𝒅𝒄
𝒏𝟒 = 𝟏 Cell 4 𝒂 𝒃 𝒄 𝒅

𝑛!
** Total number of microstates = 𝑛𝑃 𝑟 = (𝑛−𝑟)!

Introduction 19