Degrees of freedom (physics and chemistry)

This article is about physics and chemistry. For other are degrees of freedom that contribute in a quadratic way
elds, see Degrees of freedom.
to the energy of the system. They are also variables that
contribute quadratically to the Hamiltonian.
In physics, a degree of freedom is an independent physical parameter in the formal description of the state of a
physical system. The set of all dimensions of a system
is known as a phase space, and degrees of freedom are
sometimes referred to as its dimensions.

2 Degrees of freedom of gas

molecules

Denition

A degree of freedom of a physical system refers to a (typically real) parameter that is necessary to characterize the
state of a physical system.
Consider a point particle that is free to move in three
dimensions. The location of any particle in threedimensional space can be specied by three position coordinates: x, y, and z. The direction and speed at which a
particle moves can be described in terms of three velocity components, e.g. vx, vy, and vz. If the time evolution
of the system is deterministic, where the state at one instant uniquely determines its past and future position and
velocity as a function of time, such a system will have
six degrees of freedom. If the motion of the particle is
constrained to a lower number of dimensions if, for example, the particle must move along a wire or on a xed
surface then the system will have less than six degrees of
freedom. On the other hand, a system with an extended
object that may rotate or vibrate can have more than six
degrees of freedom. A force on the particle that depends
only upon time and the particles position and velocity ts
this description.

Dierent ways of visualizing the 6 degrees of freedom of a

diatomic molecule. (CM: center of mass of the system, T:
translational motion, R: rotational motion, V: vibrational motion.)

In three-dimensional space, three degrees of freedom are

associated with the movement of a particle. A diatomic
gas molecule thus has 6 degrees of freedom. This set may
be decomposed in terms of translations, rotations, and vibrations of the molecule. The center of mass motion of
the entire molecule accounts for 3 degrees of freedom.
In addition, the molecule has two rotational degrees of
motion and one vibrational mode. The rotations occur
around the two axes perpendicular to the line between
the two atoms. The rotation around the atomatom bond
is not a physical rotation. This yields, for a diatomic
molecule, a decomposition of:

In mechanics, a point particle's state at any given time can

be described with position and velocity coordinates in the
Lagrangian formalism, or with position and momentum
coordinates in the Hamiltonian formalism.
Similarly, in statistical mechanics, a degree of freedom
is a single scalar number describing the microstate of a
system.[1] The specication of all microstates of a system
is a point in the systems phase space.

A degree of freedom may be any useful property that is

not dependent on other variables. For example, in the 3D
ideal chain model, two angles are necessary to describe 3N = 6 = 3 + 2 + 1.
each monomers orientation.
For a general (non-linear) molecule with N > 2 atoms, all
In statistical mechanics and thermodynamics, it is often 3 rotational degrees of freedom are considered, resulting
useful to specify quadratic degrees of freedom. These in the decomposition:
1

4 QUADRATIC DEGREES OF FREEDOM

3N = 3 + 3 + (3N 6)
which means that an N-atom molecule has 3N 6 vibrational degrees of freedom for N > 2. In special cases,
such as adsorbed large molecules, the rotational degrees
of freedom can be limited to only one.[2]

If E = X14 + X24 , then the two degrees

of freedom are independent.
If E = X14 + X1 X2 + X24 , then the two
degrees of freedom are not independent.
The term involving the product of X1 and
X2 is a coupling term, that describes an
interaction between the two degrees of
freedom.

As dened above one can also count degrees of freedom

using the minimum number of coordinates required to
For i from 1 to N, the value of the ith degree of freedom
specify a position. This is done as follows:
X is distributed according to the Boltzmann distribution.
Its probability density function is the following:
1. For a single particle we need 2 coordinates in a 2-D
plane to specify its position and 3 coordinates in 3-D
E
i
plane. Thus its degree of freedom in a 3-D plane is
e kB T
pi (Xi ) =
3.
E
i
dXi e kB T
2. For a body consisting of 2 particles (ex. a diatomic
molecule) in a 3-D plane with constant distance be- In this section, and throughout the article the brackets
tween them (lets say d) we can show (below) its de- denote the mean of the quantity they enclose.
grees of freedom to be 5.
The internal energy of the system is the sum of the average energies associated to each of the degrees of freedom:
Lets say one particle in this body has coordinate (x1 , y1 ,
z1 ) and the other has coordinate (x2 , y2 , z2 ) with z2 unN

known. Application of the formula for distance between

E
=
Ei .
two coordinates
i=1

d=

(x2 x1 )2 + (y2 y1 )2 + (z2 z1 )2

4 Quadratic degrees of freedom

results in one equation with one unknown, in which we

can solve for z2 . One of x1 , x2 , y1 , y2 , z1 , or z2 can be A degree of freedom X is quadratic if the energy terms
associated to this degree of freedom can be written as
unknown.
Contrary to the classical equipartition theorem, at room
temperature, the vibrational motion of molecules typically makes negligible contributions to the heat capacity. This is because these degrees of freedom are frozen
because the spacing between the energy eigenvalues exceeds the energy corresponding to ambient temperatures
(kBT). In the following table such degrees of freedom
are disregarded because of their low eect on total energy. However, at very high temperatures they cannot be
neglected.

Independent degrees of freedom

The set of degrees of freedom X1 , ... , XN of a system is

independent if the energy associated with the set can be
written in the following form:

E=

Ei (Xi ),

E = i Xi2 + i Xi Y
where Y is a linear combination of other quadratic degrees of freedom.
example: if X1 and X2 are two degrees of freedom, and
E is the associated energy:
If E = X14 + X13 X2 + X24 , then the two
degrees of freedom are not independent
and non-quadratic.
If E = X14 + X24 , then the two degrees of freedom are independent and
non-quadratic.
If E = X12 +X1 X2 +2X22 , then the two
degrees of freedom are not independent
but are quadratic.
If E = X12 + 2X22 , then the two degrees of freedom are independent and
quadratic.

i=1

For example, in Newtonian mechanics, the dynamics of

a system of quadratic degrees of freedom are controlled
example: if X1 and X2 are two degrees of freedom, and by a set of homogeneous linear dierential equations with
constant coecients.
E is the associated energy:
where E is a function of the sole variable X.

4.1

Quadratic and independent degree of 6

freedom

X1 , ... , XN are quadratic and independent degrees of

freedom if the energy associated to a microstate of the
system they represent can be written as:

E=

i Xi2

i=1

4.2

Equipartition theorem

In the classical limit of statistical mechanics, at

thermodynamic equilibrium, the internal energy of a system of N quadratic and independent degrees of freedom
is:

U = E = N

kB T
2

Here, the mean energy associated with a degree of freedom is:

Ei =

dXi i Xi2 pi (Xi ) =

kB T
Ei =
2

i Xi2

dXi i Xi2 e kB T
X2

i i
dXi e kB T

x2

dx x2 e 2
kB T
=

x2

2
dx e 2

Since the degrees of freedom are independent, the

internal energy of the system is equal to the sum of the
mean energy associated with each degree of freedom,
which demonstrates the result.

Generalizations

The description of a systems state as a point in its phase

space, although mathematically convenient, is thought to
be fundamentally inaccurate. In quantum mechanics, the
motion degrees of freedom are superseded with the concept of wave function, and operators which correspond
to other degrees of freedom have discrete spectra. For
example, intrinsic angular momentum operator (which
corresponds to the rotational freedom) for an electron or
photon have only two eigenvalues. This discreteness becomes apparent when action has an order of magnitude
of the Planck constant, and individual degrees of freedom can be distinguished.

References

[1] Reif, F. (2009). Fundamentals of Statistical and Thermal

Physics. Long Grove, IL: Waveland Press, Inc. p. 51.
ISBN 1-57766-612-7.
[2] Thomas Waldmann, Jens Klein, Harry E. Hoster, R.
Jrgen Behm (2012), Stabilization of Large Adsorbates by Rotational Entropy: A Time-Resolved VariableTemperature STM Study (in German), ChemPhysChem:
pp. n/an/a, doi:10.1002/cphc.201200531

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