Course No.

Phy- 2201(A), Statistical Mechanics and Radiation, Physics Discipline, KU

Chapter – 2
Phase Space

Md. Shohel Parvez

Associate Professor
Physics Discipline, Khulna University, Khulna
Degrees of freedom
The total number of independent variables required to describe
completely the state of motion of a body are called its degrees of
freedom.
If an ant moving along a straight line, it has only one degree of
freedom. If it moves on a plane then it has two degrees of freedom.
Position space
The three dimensional space in which the location of a particle is
completely given by the three position co-ordinates is known as position
space.
A small element in position space is denoted by volume element dV
and is expressed as
 𝑑𝑉 = 𝑑𝑥𝑑𝑦𝑑𝑧
Momentum space
The momentum of the particle is completely specified by the three
mutually perpendicular momentum co-ordinates 𝑃𝑥 , 𝑃𝑦 𝑎𝑛𝑑 𝑃𝑧 in three
dimensional space known as momentum space and the small element in
momentum space is given by 𝑑𝑃𝑥 , 𝑑𝑃𝑦 𝑎𝑛𝑑 𝑑𝑃𝑧 .
If m is the mass of the particle moving along with velocity V its
momentum 𝑃 = 𝑚𝑉.
The three components of momentum are
𝑃𝑥 = 𝑚𝑉𝑥 , 𝑃𝑦 = 𝑚𝑉𝑦 𝑎𝑛𝑑 𝑃𝑧 = 𝑚𝑉𝑧
Phase space
A combination of position space and momentum space is known as
phase space. Thus phase space has six dimensions i.e. three position co-
ordinates and three momentum co-ordinates. All mutually perpendicular
to each other.
A small element in phase space is denoted by 𝑑𝜏 and is given by

𝑑𝜏 = 𝑑𝑥 𝑑𝑦 𝑑𝑧 𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧

Mu (𝝁) space
A six dimensional space for a single particle is called molecular
phase space or mu space. Since 6 dimensional diagram can not be drawn
phase space is purely a theoretical concept.
According to uncertainty principle
 𝑑𝑥 𝑑𝑃𝑥 ≃ ℎ
𝑑𝑦 𝑑𝑃𝑦 ≃ ℎ
𝑑𝑧 𝑑𝑃𝑧 ≃ ℎ
∴ 𝑑𝑥 𝑑𝑃𝑥 𝑑𝑦 𝑑𝑃𝑦 𝑑𝑧 𝑑𝑃𝑧 = ℎ3
𝑑𝑥 𝑑𝑦 𝑑𝑧 𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧 = ℎ3
Here, 𝑑𝑥 𝑑𝑦 𝑑𝑧 𝑑𝑃𝑥 𝑑𝑃𝑦 𝑑𝑃𝑧 represents the volume of each state
𝑑𝜏.
So in phase space (mu), the co-ordinates of a particle can be specified
only to the extent that lying within an element of phase space of volume
ℎ3
The Γ- space (gamma space)
Gamma space is a 6N dimensional phase space representation in
 which a single point represents a state of entire N particle system and
is referred as the representative point. The Γ-space representation is
mathematically more difficult to handle. If an ensemble is to be
represented, this 6N – dimensional representation alone is applicable.
The Γ- space is considered to be a conceptual Euclidean space, having
2fN rectangular axes.
Ensemble
If we have a collection of particles, we shall refer to a single as a
system and the collection of particles as a whole system is assembly. So
an ensemble is defined as a collection of a very large number of
assemblies which are essentially independent of one another, but which
have been made macroscopically as identical as possible. By being
 macroscopically identical, we mean that each assembly is
characterized by the same values of set of macroscopic parameters which
uniquely determine the equilibrium state of assembly.
By definition of ensemble,
Single particle → System
Collection of particle → Assembly
Collection of assemblies → Ensemble
There are three types of ensemble
1. Microcanonical ensemble
2. canonical ensemble
3. Grand – canonical ensemble
Micro canonical ensemble
The microcanonical ensemble is a collection of a essentially
independent assemblies having the same energy E, Volume V and
number of particles N, all the particles are of the same type.
The individual assemblies are separated by rigid impermeable and
well insulated walls, such that the values of E, V and N are not affected
by the presence of other systems.

E,V,N E,V,N

E,V,N E,V,N

Figure represents symbolically a micro-canonical ensemble

Canonical ensemble
The canonical ensemble is a collection of essentially independent
assemblies having same temperature T, Volume V, and Number of
identical particles N. To assume ourselves that all the assemblies have
the same type.
T,V,N T,V,N

T,VN T,V,N

Figure represents symbolically a canonical ensemble.

The individual assemblies are separated by rigid impermeable but

diathermic walls. Since energy can be exchanged between the
assemblies, they will reach a common temperature.
Grand canonical ensemble
The grand canonical ensemble is collection of essentially
independent assemblies having the same temperature T, Volume V and
chemical potential 𝜇.

T,V,𝝁 T,V,𝝁

T,V,𝝁 T,V,𝝁

Figure represents symbolically a grand canonical ensembles.

The individual ensembles are separated by rigid, impermeable and

diathermic walls.
Probability density
The condition of an ensemble at any time, can be specified by the
density ρ with which the phase point distributed over the phase space. It
is called probability density or density of distribution or distribution
function.
The density of distribution
𝜌 = 𝜌(𝑞1 , 𝑞2 … … … … … 𝑞𝑓 , 𝑝1 , 𝑝2 , … … … … 𝑝𝑓 , 𝑡)
𝜌 = 𝜌 𝑞, 𝑝, 𝑡 … … … … … … … . (1)
Liouvilli's theorem
Liouville’s theorem states that
“ The rate of change of density of phase points in a phase space with
time is zero”
 Proof
Let us consider a phase space of volume ω enclosed by a surface s.
The rate of increase of phase points in this volume ω, with time is
given by,

.
𝜕
𝜌𝑑𝜔 … … … … . (1)
𝜕𝑡
𝑤

𝑑𝑡
𝑣.
S 𝑑𝑆
w

Fig: 1
 Where, 𝜕𝜔 = 𝜕𝑞 3𝑁 𝜕𝑝3𝑁
𝜌 = 𝜌 𝑞, 𝑝, 𝑡
The rate at which the phase points flow out at across the boundary S
is given by,

− 𝜌𝑣𝑑𝑠 … … … … … … . . (2)
𝑆
Where 𝑣 is the velocity vector at the representation points.
Applying divergence theorem,

. .

− 𝜌𝑣 𝑑𝑠 = − 𝑣 𝜌𝑣 𝑑𝜔 … … … … . (3)
𝑆 𝑤
 Since there is no source and sinks, the total no of phase points must
be conserved. From equation (1) and (3) we have,

.
𝜕𝜌
{ + 𝑣(𝜌𝑣)}𝑑𝜔 = 0
𝜕𝑡
𝜔

𝜕𝜌
+ 𝑣 𝜌𝑣 = 0 … … … … … . (4)
𝜕𝑡
Equation (4) is known as equation of continuity. Here we consider,
𝑥𝑖 = (𝑞𝑖 , 𝑝𝑖 )
𝑣 = 𝑥𝑖 = 𝑞𝑖 , 𝑝𝑖
Now from equation (4)
From equation (4)

3𝑁
𝜕𝜌 𝜕 𝜕
+ + 𝜌𝑣 = 0
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖
𝑖=1

3𝑁
𝜕𝜌 𝜕 𝜕
+ (𝜌𝑞𝑖 ) + (𝜌𝑝𝑖 ) = 0
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖
𝑖=1

3𝑁
𝜕𝜌 𝜕𝑞𝑖 𝜕𝜌 𝜕𝑝𝑖 𝜕𝜌
+ 𝜌+ 𝑞𝑖 + 𝜌+ 𝑝𝑖 = 0
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑞𝑖 𝜕𝑝𝑖 𝜕𝑝𝑖
𝑖=1

3𝑁 3𝑁
𝜕𝜌 𝜕𝜌 𝜕𝜌 𝜕𝑞𝑖 𝜕𝑝𝑖
+ [ 𝑞𝑖 + 𝑝𝑖 ] + 𝜌 + =0 … … . . (5)
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖 𝜕𝑞𝑖 𝜕𝑝𝑖
𝑖=1 𝑖=1
From Hermitian equation

𝜕𝐻(𝑞𝑖 , 𝑝𝑖 )
𝑞𝑖 =
𝜕𝑝𝑖

𝜕𝐻 𝑞𝑖 , 𝑝𝑖
𝑝𝑖 = − } … … … … (6)
𝜕𝑞𝑖
Where H is the total energy of the system.

𝜕𝑞𝑖 𝜕2𝐻
=
𝜕𝑞𝑖 𝜕𝑝𝑖 𝜕𝑞𝑖

𝜕𝑝𝑖 𝜕2𝐻 𝜕2𝐻

=− =−
𝜕𝑝𝑖 𝜕𝑞𝑖 𝜕𝑝𝑖 𝜕𝑝𝑖 𝜕𝑞𝑖

𝜕𝑞𝑖 𝜕𝑝𝑖
+ =0 … … … … … … … … (7)
𝜕𝑞𝑖 𝜕𝑝𝑖
Hence equation (5) becomes

3𝑁
𝜕𝜌 𝜕𝜌 𝜕𝜌
+ 𝑞𝑖 + 𝑝𝑖 = 0
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖
𝑖=1

3𝑁
𝜕𝜌 𝜕𝜌 𝜕𝐻 𝜕𝜌 𝜕𝐻
+ − =0
𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖 𝜕𝑝𝑖 𝜕𝑞𝑖
𝑖=1

𝜕𝜌
+ 𝜌, 𝐻 = 0 ……….. 8
𝜕𝑡
Again 𝜌 is a function of 𝑞, 𝑝, 𝑡 and 𝑝, 𝑞 are function of t.

𝜕𝜌 𝜕𝜌 𝜕𝜌 𝜕𝑞 𝜕𝜌 𝜕𝑝
= + +
𝜕𝑡 𝜕𝑡 𝜕𝑞 𝜕𝑡 𝜕𝑝 𝜕𝑡
 𝜕𝜌 𝜕𝜌 𝜕𝜌 𝜕𝜌
= + 𝑞+ 𝑝
𝜕𝑡 𝜕𝑡 𝜕𝑞 𝜕𝑝
Generating this,

3𝑁 3𝑁
𝜕𝜌 𝜕𝜌 𝜕𝜌 𝜕𝜌
= + 𝑞𝑖 + 𝑝𝑖 … … … … . (9)
𝜕𝑡 𝜕𝑡 𝜕𝑞𝑖 𝜕𝑝𝑖
𝑖=1 𝑖=1
Now from (6) and (9)

𝜕𝜌 𝜕𝜌
= + 𝜌, 𝐻 = 0
𝜕𝑡 𝜕𝑡
𝜕𝜌
i.e. = 0 where 𝜌, 𝐻 stands for position bracket and this equation
𝜕𝑡

is known as Liovilli’s theorem.

Fundamental postulates of statistical mechanics
1. Any gas under consideration may be considered to be composed
of large number of molecules which are constantly in motion and
behave like very small elastic sphere.
2. All the cells in phase space are of equal size.
3. The equilibrium state of a gas corresponds to the macrostate of
the maximum probability.
4. The total number of molecules are constant. This is in accordance
with the principle of conservation of matter. If 𝑛1 is the no of
molecules in cell 1, 𝑛2 is the no of molecules in cell 2 and so on.
Then 𝑛1 + 𝑛2 + … … . . +𝑛𝑖 + ⋯ . . = 𝑛𝑖 = 𝑛 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
5. The total energy of the system is constant. This is in accordance
 with the principle of conservation of energy of the system. If 𝐸1 is the
energy of each particles in cell 1, 𝐸2 is the energy of each particles in
cell 2 and so on. Then

𝐸1 𝑛1 + 𝐸2 𝑛2 + ⋯ … … . . +𝐸𝑖 𝑛𝑖 = 𝐸𝑖 𝑛𝑖 = 𝐸 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Uses of Ensemble
We have classified ensembles into three main types. Each type
corresponds to a different experimental situation. In fact, the three
ensembles which we have introduced are only examples of the infinite
number of ensembles that can be considered. These three are particularly
useful for two main reasons.
1. They correspond approximately to the types of thermodynamic
measurements most frequently made in practice.
2. In large assemblies, it is useful to find that the values of
thermodynamic quantities are not very sensitive to the method of
measurements. For example, in the measurements of specific heat
of a liquid of known mass and thus known particle number, at
temperatures far below the boiling point, it matters very little
whether the liquid is isolated at constant temperatures so that the
number of systems is fixed as in a microcanonical ensembles or
in equilibrium with its vapour so that the number of systems can
fluctuate as in grand canonical ensemble.
Thank you