Question

Briefly explain the main differences of heat capacity approaches of solid between Einstein, Debye and classic thermodynamic model.

Answer 1

Einstein solid

The original theory proposed by Einstein in 1907 has great historical relevance. The heat capacity of solids as predicted by the empirical Dulong–Petit law was required by classical mechanics, the specific heat of solids should be independent of temperature. But experiments at low temperatures showed that the heat capacity changes, going to zero at absolute zero. As the temperature goes up, the specific heat goes up until it approaches the Dulong and Petit prediction at high temperature.

The Einstein solid is a model of a solid based on two assumptions:

1. Each atom in the lattice is an independent 3D quantum harmonic oscillator
2. All atoms oscillate with the same frequency (contrast with the Debye model).

While the assumption that a solid has independent oscillations is very accurate, these oscillations are sound waves or phonons, collective modes involving many atoms. In the Einstein model, however, each atom oscillates independently. Einstein was aware that getting the frequency of the actual oscillations would be difficult, but he nevertheless proposed this theory because it was a particularly clear demonstration that quantum mechanics could solve the specific heat problem in classical mechanics.

Debye model

In thermodynamics and solid state physics, the Debye model is a method developed by Peter Debye in 1912 for estimating the phonon contribution to the specific heat (heat capacity) in a solid.It treats the vibrations of the atomic lattice (heat) as phonons in a box, in contrast to the Einstein model, which treats the solid as many individual, non-interacting quantum harmonic oscillators. The Debye model correctly predicts the low temperature dependence of the heat capacity, which is proportional to T3 – the Debye T3 law. Just like the Einstein model, it also recovers the Dulong–Petit law at high temperatures. But due to simplifying assumptions, its accuracy suffers at intermediate temperatures.

The Debye model is a solid-state equivalent of Planck's law of black body radiation, where one treats electromagnetic radiation as a photon gas. The Debye model treats atomic vibrations as phonons in a box (the box being the solid). Most of the calculation steps are identical as both are examples of a massless Bose gas with linear dispersion relation.

Classical thermodynamic model

Classical thermodynamics is the description of the states of thermodynamic systems at near-equilibrium, that uses macroscopic, measurable properties. It is used to model exchanges of energy, work and heat based on the laws of thermodynamics. The qualifier classical reflects the fact that it represents the first level of understanding of the subject as it developed in the 19th century and describes the changes of a system in terms of macroscopic empirical (large scale, and measurable) parameters. A microscopic interpretation of these concepts was later provided by the development of statistical mechanics.