Skip to main content
Library homepage
 
Chemistry LibreTexts

Isothermal-isobaric and grand canonical ensembles

  • Page ID
    5258
  • \( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

    Also useful are the isothermal-isobaric and grand canonical ensembles, which are defined just as they are for the classical cases:

    • isothermal-isobaric:

    \[\Delta(N,P,T) = \int_0^{\infty}dV e^{-\beta PV} Q(N,V,T) =\int_0^{\infty} dV {\rm Tr}(e^{-\beta (H+PV)})\]

    • grand canonical ensembles

    \[ {\cal Z}(\mu,V,T) = \sum_{N=0}^{\infty}e^{\beta \mu N}Q(N,V,T) = \sum_{N=0}^{\infty} {\rm Tr}(e^{-\beta (H-\mu N)})\]

    Contributors and Attributions

    Mark Tuckerman (New York University)


    Isothermal-isobaric and grand canonical ensembles is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.

    • Was this article helpful?