Debye's Derivation
Actually, Debye derived his equation somewhat differently and more simply. Using the solid mechanics of a continuous medium, he found that the number of vibrational states with a frequency less than a particular value was asymptotic to
in which is the volume and is a factor which he calculated from elasticity coefficients and density. Combining this with the expected energy of a harmonic oscillator at temperature T (already used by Einstein in his model) would give an energy of
if the vibrational frequencies continued to infinity. This form gives the behavior which is correct at low temperatures. But Debye realized that there could not be more than vibrational states for N atoms. He made the assumption that in an atomic solid, the spectrum of frequencies of the vibrational states would continue to follow the above rule, up to a maximum frequency chosen so that the total number of states is :
Debye knew that this assumption was not really correct (the higher frequencies are more closely spaced than assumed), but it guarantees the proper behavior at high temperature (the Dulong–Petit law). The energy is then given by:
-
- where is .
where is the function later given the name of third-order Debye function.
Read more about this topic: Debye Model