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The grand canonical partition function applies to a grand canonical ensemble, in which the system can exchange both heat and particles with the environment, at fixed temperature, volume, and chemical potential. Other types of partition functions can be defined for different circumstances; see partition function (mathematics) for
Let n denote a complete set of (discrete) quantum numbers for specifying single-particle states (for example, for the particle in a box problem, take n to be the quantized wave vector of the wavefunction.) For simplicity, consider a system composed of two particles that are not interacting with each other.
The partition function is commonly used as a probability-generating function for expectation values of various functions of the random variables. So, for example, taking β {\displaystyle \beta } as an adjustable parameter, then the derivative of log ( Z ( β ) ) {\displaystyle \log(Z(\beta ))} with respect to β {\displaystyle \beta }
In either case, the partition function may be solved exactly using eigenanalysis. If the matrices are all the same matrix W , the partition function may be approximated as the N th power of the largest eigenvalue of W , since the trace is the sum of the eigenvalues and the eigenvalues of the product of two diagonal matrices equals the product ...
In other words, each single-particle level is a separate, tiny grand canonical ensemble. By the Pauli exclusion principle, there are only two possible microstates for the single-particle level: no particle (energy E = 0), or one particle (energy E = ε). The resulting partition function for that single-particle level therefore has just two terms:
A particle speed probability distribution indicates which speeds are more likely: a randomly chosen particle will have a speed selected randomly from the distribution, and is more likely to be within one range of speeds than another. The kinetic theory of gases applies to the classical ideal gas, which is an idealization of real gases.
In statistical mechanics, the translational partition function, is that part of the partition function resulting from the movement (translation) of the center of mass. For a single atom or molecule in a low pressure gas, neglecting the interactions of molecules , the canonical ensemble q T {\displaystyle q_{T}} can be approximated by: [ 1 ]
The terms in the bracket give the total partition function of the adsorbed molecules by taking a product of the individual partition functions (refer to Partition function of subsystems). The 1 / N A ! {\displaystyle 1/N_{A}!} factor accounts for the overcounting arising due to the indistinguishable nature of the adsorbates.
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