Canonical Partition Function
Table of Contents
The canonical partition function, denoted by \( \small Z\ \), is a fundamental concept in statistical mechanics. It is a useful tool that can tell us the properties of the system, such as the probability that the system is in a particular state, the average energy of the system, and the heat capacity of the system.
For a classical, discrete canonical ensemble at a temperature \( \small T\ \), the canonical partition function is given by:
Partition function #
$$ Z = \sum_{i} e^{-\beta E_i} $$
Where:
- \( \small Z\ \) is the canonical partition function,
- \( \small E_i\ \) is the energy of the \( \small i\ \)-th microstate,
- The sum is taken over all possible microstates of the system, and
- \( \small \beta = \frac{1}{k_B T}\ \) is the thermodynamic beta with \( \small k_B\ \) being the Boltzmann constant and \( \small T\ \) being the temperature.
Probability of a state #
The probability of the system having energy E_i is given by:
$$ P(E_i) = \frac{e^{-\beta E_i}}{Z} $$
Where:
- \( \small P(E_i)\ \) is the probability of the system being in the \( \small i\ \)-th microstate, and
- \( \small Z\ \) is the canonical partition function described above.
Other quantities #
A few useful properties can be derived from the partition function. For example, the average energy of the system is given by:
$$ \langle E \rangle =\frac{1}{Z}\frac{\partial Z}{\partial \beta} = -\frac{\partial \ln Z}{\partial \beta} = k_B T^2 \frac{\partial \ln Z}{\partial T}$$
Next, the expectation value of the energy squared is given by:
$$ \langle E^2 \rangle = \frac{1}{Z}\frac{\partial^2 Z}{\partial \beta^2} $$
Combining these two, we can get the mean square fluctiation of the energy:
$$ \langle \Delta E^2 \rangle = \langle E^2 \rangle - \langle E \rangle^2 = - \frac{\partial \langle E \rangle}{\partial \beta} $$ k Finally, the heat capacity of the system is given by:
$$ C_v(T) = \frac{1}{k_B T^2} \langle \Delta E^2 \rangle$$
Sources #
- Wikipedia
- My professor’s slides