Molecular Statistics

※ Degrees of freedom:
Degrees of freedom: the total number of independent variables

whose values have to be specified for a complete description

of the system.

(A) One atom: In the context of molecular motion these are the

spatial coordinates of all the particles. Since we need

three coordinates to describe the position of an atom, we

say the atom has three degrees of freedom.

(B) Diatomic molecule: If the atoms are not bound to one

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 another, there will be no relation among the coordinates of

the two atoms. On the other hand, when the two atoms are

bound, the displacement of each other is coupled to the

other. The result is to give three translational, one

vibrational, and two rotational degrees of freedom for the

molecule. The vibrational and rotational degrees of

freedom are also referred to as internal degrees of freedom.

(C) Polyatomic molecule with N atoms:

(i) Linear molecule: The 3N degrees of freedom of the

atoms become three translational degrees of freedom

and (3N-3) internal degrees of freedom. By analogy

with diatomic molecules, we expect two rotational

degrees of freedom for any linear polyatomic molecule

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 (e.g. CO2 and C2H2). The remaining (3N-5) internal

coordinates must correspond to vibrations.

(ii) Bent molecule: A bent molecule loses a vibrational

degree of freedom while gaining a rotational degree of

freedom. Therefore, a nonlinear polyatomic molecule

has three rotational degrees of freedom, hence (3N-6)

vibrational degrees of freedom.

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 e.g. vibrational motions for CO2 and H2O:

Degrees of Linear Bent

Atom

freedom polyatomic polyatomic

Translational 3 3 3

Vibrational 0 3N-5 3N-6

Rotational 0 2 3

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※ Molecular energies:
n 2h 2
(A) Translational energies: En 
8m
for one axis.

Where n = 1, 2, 3…., is the translational quantum number,

m is the mass of the particle, and l is the distance between

the walls.

Since a particle has three translational degrees of freedom,

the total translational energy is given by

h 2  nx2 n y nz2 
2

En     
8m  2x 2y 2z 

Where lx, ly, and lz denote the dimensions of the box.

(B) Vibrational energies:

For a diatomic molecule, the vibrational energy is given

 2  by:
E  h   1
V

Where h called Planck’s constant, 6.626  10 J  sec

34
is

Andνis the frequency of oscillation. The symbolυdenotes

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 the vibrational quantum number which can have only

integer values, 0, 1, 2, ….

(C) Rotational energies:

Rotational energies of diatomic molecules are represented

2
h
E  J  J  1
8 2 I
J

quite accurately by the quantum

formula:

where J, which is restricted to values of 0, 1, 2, .. is called

the rotational quantum number. The moment of inert I is

related to the bond length r of the diatomic molecule by

I = mrr2. The mr is called the reduced mass, which is

obtained from the mass of the two atoms:

mm
m  1 2

m m
r
1 2

※ The origin of quantum mechanics:

The origin of atomic structure:

Three great discoveries:

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 J. J. Thomson’s discovery:

 
To measure e m value using magnet to deflect e- beam in

1897.

 R. A. Millikan’s discovery:

To determine electron charge using oil drop experiment in

1909.

 E. Rutherford’s discovery:

To define atomic structure usingαparticle to strike a thin

foil of gold in 1911.

Three important discoveries lead to following summary:

 Each atom consists of a very small nucleus composed of

protons and neutrons, which is encircled by moving

electron.

 Both electrons and protons are electrically charged, the

charge magnitude being 1 . 6  10 19

C, which is negative in

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 sign for electrons and positive for protons; neutrons are

electrically neutral.

 The masses for proton and neutrons have approximately

the same value, 1 . 67  10 2 7

kg . The mass of electron is

9 . 11  10 31 kg .

 Each chemical element is characterized by the number of

protons in the nucleus, or the atomic number (Z). For an

electrically neutral, the atomic number is equal to the

number of electrons.

 The atomic mass (M) of a specific atom may be expressed

as the sum of the masses of protons and neutrons within

the nucleus, i.e. M=Z+N.

The quantization of energy:

Two important phenomena:

 Black-body radiation:

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 A black-body radiator consists of a block of material

having an internal cavity connected to the outside

surface of the block by a small hole.

 The radiation emerging from the hole when the block

is raised to a uniform temperature is called black-body

radiation.

 The spectra radiation depends on wavelength.

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  Planck proposed the concept of energy quantized in

1900.

 Photon with energy in h .

 Photoelectric effect:

 The electrons come out when a light is shining onto a

metal.

 The frequency of light controls whether or not

electrons are emitted, but not light intensity.

 The number of electrons emitted is proportional to the

intensity.

 Photon with energy in h and the kinetic energy of the

electron emitted is determined by h  1 2 mv  w .

2

 Confirm Planck’s concept of energy quantized.

※Boltzmann distribution:

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 The populations of energy levels:

Since any molecule can only posses certain energies at a

given temperature, each of molecules can distribute over all

the available energy levels. Although we cannot keep track

of the energy state of a single molecule, we can speak of the

average numbers of molecules in each state, and these

average numbers are constant in time so long as the

temperature remains the same. The average number of

molecules in a state is called the population of the state.

Only the lowest energy level is ocupied at T = 0 K.

Raising the temperature excites some molecules into higher

energy levels, and more and more levels become accessible

as the temperature is raised further. Nevertheless, whatever

the temperature, there is always a higher population in a state

of low energy than one of high energy.

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 Boltzmann distribution:

The population in state n with energy En is determined by

the temperature T according to the Boltzmann distribution:

En

N Ne
n 0
k BT

This formula was derived by Ludwig Boltzmann towards the

end of the 19th century. According to this formula, the

population ratio of the numbers of particles in various states

with energies Ei and Ej is determined by

 Ei  E j 
Ni 
e k BT

Nj

The fundamental constant kB is called Boltzmann’s constant,

k  1.38  10  23 J
B
K. Boltzmann’s constant is replaced by

the gas constant, R=NAkB, if the energies in the Boltzmann

distribution are replaced by molar energies.

The possibility fi of molecules occupying the i-th state is

Ei

N N e k BT

f   i
 i
Ei
N  N e
i 
k BT
i
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determined to be

In consideration of degeneracy, the equation is rewrriten to

be:

The sum in the denominator is called the partition

Ei

N N ge k BT

f  i
  i i
Ei
N N g e
i 
k BT
i
i

function, which means as “sum over states”.

The Boltzmann distribution law is written as

 Ei  E j 
Ni g 
 e i k BT

Nj
g j

If fi are the fractions of molecules in different quantum states,

the average energy per particle <E> is given by

E fE
i i

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