How does pressure fluctuate in equilibrium? (Q1631484)

Pressure in equilibrium statistical mechanics of finite systems can be defined in two ways. ``Mechanical pressure'' is defined in terms of averages of momentum transfer. An alternative definition starts from the thermodynamic relations $P = T \frac{\partial S}{\partial V}(E,V,N)$, $T = \frac{\partial S}{\partial E}(E,V,N)$, where $P, T, S, E, V, N$ stand respectively for the pressure, temperature, entropy, energy, volume, and number of particles of the system. The expressions for $T$ and $p$ are then evaluated at random values of the energy and volume (in the NpT-ensemble). The two definitions of the pressure give rise to two different random variables. The main point of the article is a comparison of the variances of these two variables in the constant pressure ensemble: the variance of the mechanical pressure is larger. The article includes a discussion of an idealized experimental measurement of pressure fluctuations.