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Probabilistic Foundations of Statistical Mechanics: A Bayesian Approach

We examine the fundamental aspects of statistical mechanics, dividing the problem into a discussion purely about probability, which we analyse from a Bayesian standpoint. We argue that the existence of a unique maximising probability distribution $\{p(j\vert K)\}$ for states labelled by $j$ given data $K$ implies that the corresponding maximal value of the information entropy $σ(\{(p_j\vert K)\}) = -\sum_j (p_j \vert K)\ln{(p_j\vert K)}$ depends explicitly on the data at equilibrium and on the Hamiltonian of the system. As such, it is a direct measure of our uncertainty about the exact state of the body and can be identified with the traditional thermodynamic entropy. We consider the well known microcanonical, canonical and grand canonical methods and ensure that the fluctuations about mean values are generally minuscule for macroscopic systems before identifying these mean values with experimental observables and thereby connecting to many standard results from thermodynamics. Unexpectedly, we find that it is not generally possible for a quantum process to be both isentropic and reversibly adiabatic. This is in sharp contrast to traditional thermodynamics where it is assumed that isentropic, reversible adiabatic processes can be summoned up on demand and easily realised. By contrast, we find that linear relations between pressures $P_j$ and energies $E_j$ are necessary and sufficient conditions for a quasi-static and adiabatic change to be isentropic, but, of course, this relationship only holds for a few especially simple systems, such as the perfect gas, and is not generally true for more complicated systems. By considering the associated entropy increases up to second order in small volume changes we argue that the consequences are in practice negligible.