Quantum Thermodynamic Integrability for Canonical and Noncanonical Statistics

We extend the Carathéodory principle of the second law to quantum thermodynamics, where energy levels depend on macroscopic variables such as volume and magnetic field. This extension introduces the concept of quantum thermodynamic integrability (QTI), providing an alternative foundation for statistical mechanics. QTI is characterized by the path independence of work and heat within the thermodynamic manifold, locally described by energy levels and specific thermodynamic parameters. Within this framework, temperature naturally emerges as an integrating factor, enabling the derivation of both canonical and noncanonical states from the entropy integrable equations based on QTI. Notably, noncanonical states, which become particularly significant outside the thermodynamic limit, reveal the existence of informational correlations in finite-size thermodynamic systems.