Foundations of Nonequilibrium Statistical Mechanics in Extended State Space

• Published in: Foundations (Basel) 2023-08, Vol.3 (3), p.419-548
• Main Author: Gujrati, Purushottam Das
• Format: Article
• Language: English
• Subjects: internal variables; macrostates; microstates; nonequilibrium; system-intrisic and medium-intrisic quantities; uniqueness
• ISSN: 2673-9321; 2673-9321
• DOI: 10.3390/foundations3030030

The review provides a pedagogical but comprehensive introduction to the foundations of a recently proposed statistical mechanics (μNEQT) of a stable nonequilibrium thermodynamic body, which may be either isolated or interacting. It is an extension of the well-established equilibrium statistical mechanics by considering microstates mk in an extended state space in which macrostates (obtained by ensemble averaging A^) are uniquely specified so they share many properties of stable equilibrium macrostates. The extension requires an appropriate extended state space, three distinct infinitessimals dα=(d,de,di) operating on various quantities q during a process, and the concept of reduction. The mechanical process quantities (no stochasticity) like macrowork are given by A^dαq, but the stochastic quantities C^αq like macroheat emerge from the commutator C^α of dα and A^. Under the very common assumptions of quasi-additivity and quasi-independence, exchange microquantities deqk such as exchange microwork and microheat become nonfluctuating over mk as will be explained, a fact that does not seem to have been appreciated so far in diverse branches of modern statistical thermodynamics (fluctuation theorems, quantum thermodynamics, stochastic thermodynamics, etc.) that all use exchange quantities. In contrast, dqk and diqk are always fluctuating. There is no analog of the first law for a microstate as the latter is a purely mechanical construct. The second law emerges as a consequence of the stability of the system, and cannot be violated unless stability is abandoned. There is also an important thermodynamic identity diQ≡diW ≥ 0 with important physical implications as it generalizes the well-known result of Count Rumford and the Gouy-Stodola theorem of classical thermodynamics. The μNEQT has far-reaching consequences with new results, and presents a new understanding of thermodynamics even of an isolated system at the microstate level, which has been an unsolved problem. We end the review by applying it to three different problems of fundamental interest.