Here, use has been made of , and the third law of thermodynamics. Clearly, the optimum way of verifying the results of statistical thermodynamics is to compare the theoretically predicted heat capacities with the experimentally measured values.

Classical physics, in the guise of the equipartition theorem, says that each
independent degree of freedom associated with a quadratic term in the energy
possesses an average energy in thermal equilibrium at temperature
. Consider a substance made up of molecules. Every molecular
degree of freedom contributes
,
or
, to the mean energy of the substance (with the tacit proviso
that each degree of freedom is associated with a quadratic term in the energy).
Thus, the contribution to the molar heat capacity at constant volume (we wish to
avoid the complications associated with any external work done on the substance) is

(489) |

where is the number of molecular degrees of freedom. Since large complicated molecules clearly have very many more degrees of freedom than small simple molecules, the above formula predicts that the molar heat capacities of substances made up of the former type of molecules should greatly exceed those of substances made up of the latter. In fact, the experimental heat capacities of substances containing complicated molecules are generally greater than those of substances containing simple molecules, but by nowhere near the large factor predicted by Eq. (490). This equation also implies that heat capacities are temperature independent. In fact, this is not the case for most substances. Experimental heat capacities generally increase with increasing temperature. These two experimental facts pose severe problems for classical physics. Incidentally, these problems were fully appreciated as far back as 1850. Stories that physicists at the end of the nineteenth century thought that classical physics explained absolutely everything are largely apocryphal.

The equipartition theorem (and the whole classical approximation) is only valid
when the typical thermal energy greatly exceeds the spacing between quantum
energy levels. Suppose that the temperature is sufficiently low that this
condition is not satisfied for one particular molecular degree of freedom.
In fact, suppose that is much less than the spacing between
the energy levels.
According to Sect. 7.9, in this situation the degree of freedom only contributes
the ground-state energy, , say, to the mean energy of the molecule. The
ground-state energy can be a quite complicated
function of the internal properties of the
molecule, but is certainly not a function of the temperature, since this is
a collective property of all molecules. It follows that the contribution to
the molar heat capacity is

(491) |

To make further progress, we need to
estimate the typical spacing between the quantum energy levels
associated with various degrees of freedom.
We can do this by observing the
frequency
of the electromagnetic radiation emitted and absorbed during transitions between
these energy levels. If the typical spacing between energy levels is
then
transitions between the various levels are associated with photons of
frequency , where
. We can define an *effective
temperature* of the radiation via
. If
then
, and the degree of freedom makes its
full contribution to the heat capacity. On the other hand, if
then
, and the degree of freedom is frozen out.
Table 3 lists the ``temperatures'' of various different types of radiation.
It is clear that degrees of freedom which give rise to emission or absorption
of radio or microwave radiation contribute their full
to the molar heat capacity at room temperature. Degrees of freedom which give rise to
emission or absorption in the visible, ultraviolet, X-ray, or -ray
regions of the electromagnetic spectrum are frozen out at room temperature.
Degrees of freedom which emit or absorb infrared radiation are on the border line.