Entropy, Energy, and Temperature in Small Systems: Impact of a Relative Energy Window in Microcanonical Statistical Mechanics

Abstract

Small systems consisting of a few particles are increasingly technologically relevant. In such systems, an intense debate in microcanonical statistical mechanics has been about the correctness of Boltzmann’s surface entropy versus Gibbs’ volume entropy. While the former considers states within a fixed energy window centered around the energy of the system, the latter considers all states with energy lesser than or equal to the energy of the system. Both entropies have shortcomings─while Boltzmann entropy predicts unphysical negative/infinite absolute temperatures for small systems with an unbounded energy spectrum, Gibbs entropy entirely disallows negative absolute temperatures, in disagreement with experiments. We consider a relative energy window, motivated by the Heisenberg energy-time uncertainty principle and an eigenstate thermalization time inversely proportional to the system energy. The resulting entropy ensures positive, finite temperatures for systems without a maximum limit on their energy and allows negative absolute temperatures in bounded energy spectrum systems, e.g., with population inversion. It also closely matches canonical ensemble predictions for prototypical systems, for instance, correctly describing the zero-point energy of an isolated quantum harmonic oscillator. Overall, we enable accurate thermodynamic models for isolated systems with few degrees of freedom.