The Six Degrees of Freedom of a Diatomic Molecule

​
x
y
z
θ
ϕ
r
For a diatomic molecule at sufficiently high temperatures, the equipartition of energy theorem distributes an equal portion of the energy, equal to
1
2
k
B
T
, among each quadratic term in the Hamiltonian. Here
k
B
is the Boltzmann constant and
T
is the absolute temperature. Three of the degrees of freedom are translations, two are rotations, and one is vibration. The vibrational degree of freedom contributes a total energy
k
B
T
since the associated kinetic energy and potential energy are both quadratic forms. The temperature should not be too high (say,
T≲1000
K), otherwise electronic degrees of freedom might be excited.

Details

For the translations, the kinetic energy is equal to
1
2
m
2
v
in each direction
x
,
y
, and
z
; for the rotations,
1
2
I
2
ω
for angles θ and ϕ, where
I
is the moment of inertia of the molecule and
ω
is the angular velocity. Finally, the energy associated with the vibrational degree of freedom, in the harmonic oscillator approximation, can be written as
1
2
m
2
v
r
+
1
2
k
2
(r-
r
0
)
, where
v
r
is the velocity along the direction of the chemical bond,
k
is a spring constant associated with the chemical bond,
r
is the elongation or compression, and
r
0
is the equilibrium position. Adding the energies of all six degrees gives a theoretical value for the molar heat capacity at constant volume
C
V
=
7
2
R
, where
R
is the universal gas constant.

External Links

Angular Velocity (ScienceWorld)
Potential Energy (ScienceWorld)
Kinetic Energy (ScienceWorld)
Inertia (ScienceWorld)
Degree of Freedom (ScienceWorld)
Boltzmann's Constant (ScienceWorld)
Universal Gas Constant (ScienceWorld)
Specific Heat (ScienceWorld)
Equipartition Theorem (ScienceWorld)

Permanent Citation

Enrique Zeleny
​
​"The Six Degrees of Freedom of a Diatomic Molecule"​
​http://demonstrations.wolfram.com/TheSixDegreesOfFreedomOfADiatomicMolecule/​
​Wolfram Demonstrations Project​
​Published: August 4, 2010