Finite-size normalization of the isothermal-isobaric ensemble
ID: finite-size-normalization-of-the-isothermal-isobaric-ensemble
For a classical monatomic ideal gas, direct volume integration gives . Consequently the continuous-volume ensemble has . Defining a dimensionless thermodynamic function using instead gives . The normalized volume distribution is identical, because the prefactor cancels in probabilities. Its temperature derivative nevertheless contributes to the derived enthalpy and to its heat capacity. The two conventions agree at leading extensive order, but cannot be mixed in an exact finite- fluctuation identity.
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