Grand canonical ensemble: Difference between revisions
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== Helmholtz energy and partition function == | == Helmholtz energy and partition function == | ||
The corresponding thermodynamic potential for the [[Grand canonical partition function | grand canonical partition function]] is: | The corresponding thermodynamic potential, the '''grand potential''', <math>\Omega</math>, | ||
for the [[Grand canonical partition function | grand canonical partition function]] is: | |||
: <math> \Omega = \left. A - \mu N \right. </math>, | |||
where ''A'' is the [[Helmholtz energy function]]. | |||
Using the relation | |||
:<math>\left.U\right.=TS -PV + \mu N</math> | |||
one arrives at | |||
: <math> \left. \Omega \right.= -PV</math> | |||
i.e.: | i.e.: | ||
:<math> \left. p V = k_B T \log Q_{\mu V T } \right. </math> | :<math> \left. p V = k_B T \log Q_{\mu V T } \right. </math> | ||
[[Category:Statistical mechanics]] | [[Category:Statistical mechanics]] | ||
Revision as of 15:59, 21 May 2007
Ensemble variables
- Chemical Potential,
- Volume, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. V \right. }
- Temperature, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. T \right. }
Partition Function
Classical partition function (one-component system) in a three-dimensional space: Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Q_{\mu VT} }
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Q_{\mu VT} = \sum_{N=0}^{\infty} \frac{ \exp \left[ \beta \mu N \right] V^N}{N! \Lambda^{3N} } \int d (R^*)^{3N} \exp \left[ - \beta U \left( V, (R^*)^{3N} \right) \right] }
where:
- is the number of particles
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. \Lambda \right. } is the de Broglie thermal wavelength (which depends on the temperature)
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \beta = \frac{1}{k_B T} } , with Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle k_B } being the Boltzmann constant
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. U \right. } is the potential energy, which depends on the coordinates of the particles (and on the interaction model)
- represent the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 3N} position coordinates of the particles (reduced with the system size): i.e. Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \int d (R^*)^{3N} = 1 }
Helmholtz energy and partition function
The corresponding thermodynamic potential, the grand potential, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Omega} , for the grand canonical partition function is:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Omega = \left. A - \mu N \right. } ,
where A is the Helmholtz energy function. Using the relation
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left.U\right.=TS -PV + \mu N}
one arrives at
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. \Omega \right.= -PV}
i.e.:
- Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left. p V = k_B T \log Q_{\mu V T } \right. }