Ensemble average
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In statistical mechanics, the ensemble average is defined as the mean of a quantity that is a function of the micro-state of a system (the ensemble of possible states), according to the distribution of the system on its micro-states in this ensemble.
Since the ensemble average is dependent on the ensemble chosen, its mathematical expression varies from ensemble to ensemble. However, the mean obtained for a given physical quantity doesn't depend on the ensemble chosen at the thermodynamic limit.
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[edit] Canonical ensemble average
[edit] Classical statistical mechanics
For a classical system in thermal equilibrium with its environment, the ensemble average takes the form of an integral over the phase space of the system:
- where:
- is the ensemble average of the system property A,
- β is , known as thermodynamic beta,
- H is the Hamiltonian (or energy function) of the classical system in terms of the set of coordinates qi and their conjugate generalized momenta pi, and
- dτ is the volume element of the classical phase space of interest.
The denominator in this expression is known as the partition function, and is denoted by the letter Z.
[edit] Quantum statistical mechanics
For a quantum system in thermal equilibrium with its environment, the weighted average takes the form of a sum over quantum energy states, rather than a continuous integral: