\[
c_V = \frac{\partial w}{\partial T}
\]
-in which $w$ is the energy density of the system.
+in which $w$ is the internal energy density of the system.
+In the following the contribution to the specific heat due to the
+degrees of freedom of the lattice ions is calculated.
\section{Specific heat in the classical theory of the harmonic crystal -\\
The law of Dulong and Petit}
In the classical theory of the harmonic crystal equilibrium properties
-can no longer be evaluated by simply assuming that each ion sits quitly at
+can no longer be evaluated by simply assuming that each ion sits quietly at
its Bravais lattice site {\bf R}.
From now on expectation values have to be claculated by
integrating over all possible ionic configurations weighted by
\begin{enumerate}
\item Show that the energy density can be rewritten to read:
\[
- u=-\frac{1}{V}\frac{\partial}{\partial \beta} ln \int d\Gamma \exp(-\beta H).
+ w=-\frac{1}{V}\frac{\partial}{\partial \beta} ln \int d\Gamma \exp(-\beta H).
\]
\item Show that the potential contribution to the energy
in the harmonic approximation is given by
Which parts of the integral do not contribute to $w$ and why?
\end{enumerate}
-
\section{Specific heat in the quantum theory of the harmonic crystal -\\
The Debye model}
+As found in exercise 1, the specific heat of a classical harmonic crystal
+is not depending on temeprature.
+However, as temperature drops below room temperature
+the specific heat of all solids is decreasing as $T^3$ in insulators
+and $AT+BT^3$ in metals.
+This can be explained in a quantum theory of the specific heat of
+a harmonic crystal, in which the energy density $w$ is given by
+\[
+w=\frac{1}{V}\frac{\sum_i E_i \exp(-\beta E_i)}{\sum_i \exp(-\beta E_i)}.
+\]
\begin{enumerate}
- \item
- \item
+ \item Show that the energy density can be rewritten to read:
+ \[
+ w=-\frac{1}{V}\frac{\partial}{\partial \beta} ln \sum_i \exp(-\beta E_i).
+ \]
+ \item Evaluate the expression of the energy density.
+ {\bf Hint:}
+ The energy levels of a harmonic crystal of N ions
+ can be regarded as 3N independent oscillators,
+ whose frequencies are those of the 3N classical normal modes.
+ The contribution to the total energy of a particular normal mode
+ with angular frequency $\omega_s({\bf k})$
+ ($s$: branch, ${\bf k}$: wave vector) is given by
+ $(n_{{\bf k}s} + \frac{1}{2})\hbar\omega_s({\bf k})$ with the
+ excitation number $n_{{\bf k}s}$ being restricted to integers greater
+ or equal zero.
+ The total energy is given by the sum over the energies of the individual
+ normal modes.
+ Use the totals formula of the geometric series to expcitly calculate
+ the sum of the exponential functions.
+ \item Separate the above result into a term vanishing as $T$ goes to zero and
+ a second term giving the energy of the zero-point vibrations of the
+ normal modes.
+ \item Write down an expression for the specific heat.
+ Consider a large crystal and thus replace the sum over the discrete
+ wave vectors with an integral.
+ \item Debye replaced all branches of the vibrational spectrum with three
+ branches, each of them obeying the dispersion relation
+ $w=ck$.
+ Additionally the integral is cut-off at a radius $k_{\text{D}}$
+ to have a total amount of N allowed wave vectors.
+ Determine $k_{\text{D}}$.
+ Evaluate the simplified integral and introduce the
+ Debye frequency $\omega_{\text{D}}=k_{\text{D}}c$
+ and the Debye temperature $\Theta_{\text{D}}$ which is given by
+ $\Theta_{\text{D}}=\hbar\omega_{\text{D}}$.
+ Write down the resulting expression for the specific heat.
\end{enumerate}
\end{document}