By utilizing notions from statistical mechanics, we develop a general and self-consistent theoretical framework capable of describing any weakly nonlinear optical multimode system involving conserved quantities. We derive the fundamental relations that govern the grand canonical ensemble through maximization of the Gibbs entropy at equilibrium. In this classical picture of statistical photo-mechanics, we obtain analytical expressions for the probability distribution, the grand partition function, and the relevant thermodynamic potentials. Our results universally apply to any other weakly nonlinear multimode bosonic system.
Foundations of a finite non-equilibrium statistical thermodynamics: extrinsic quantities
Abstract Statistical thermodynamics is valuable as a conceptual structure that shapes our thinking about equilibrium thermodynamic states. A cloud of unresolved questions surrounding the foundations of the theory could lead an impartial observer to conclude that statistical thermodynamics is in a state of crisis though. Indeed, the discussion about the microscopic origins of irreversibility has continued in the scientific community for more than a hundred years. This paper considers these questions while beginning to develop a statistical thermodynamics for finite non-equilibrium systems. Definitions are proposed for all of the extrinsic variables of the fundamental thermodynamic relation that are consistent with existing results in the equilibrium thermodynamic limit. The probability density function on the phase space is interpreted as a subjective uncertainty about the microstate, and the Gibbs entropy formula is modified to allow for entropy creation without introducing additional physics or modifying the phase space dynamics. Resolutions are proposed to the mixing paradox, Gibbs’ paradox, Loschmidt’s paradox, and Maxwell’s demon thought experiment. Finally, the extrinsic variables of the fundamental thermodynamic relation are evaluated as functions of time and space for a diffusing ideal gas, and the initial and final values are shown to coincide with the expected equilibrium values.
more »
« less
- Award ID(s):
- 1839370
- NSF-PAR ID:
- 10392737
- Date Published:
- Journal Name:
- Journal of Physics A: Mathematical and Theoretical
- Volume:
- 55
- Issue:
- 29
- ISSN:
- 1751-8113
- Page Range / eLocation ID:
- 295002
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
-
Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.more » « less
-
more » « less
Abstract Today’s thermodynamics is largely based on the combined law for equilibrium systems and statistical mechanics derived by Gibbs in 1873 and 1901, respectively, while irreversible thermodynamics for nonequilibrium systems resides essentially on the Onsager Theorem as a separate branch of thermodynamics developed in 1930s. Between them, quantum mechanics was invented and quantitatively solved in terms of density functional theory (DFT) in 1960s. These three scientific domains operate based on different principles and are very much separated from each other. In analogy to the parable of the blind men and the elephant articulated by Perdew, they individually represent different portions of a complex system and thus are incomplete by themselves alone, resulting in the lack of quantitative agreement between their predictions and experimental observations. Over the last two decades, the author’s group has developed a multiscale entropy approach (recently termed as zentropy theory) that integrates DFT-based quantum mechanics and Gibbs statistical mechanics and is capable of accurately predicting entropy and free energy of complex systems. Furthermore, in combination with the combined law for nonequilibrium systems presented by Hillert, the author developed the theory of cross phenomena beyond the phenomenological Onsager Theorem. The zentropy theory and theory of cross phenomena jointly provide quantitative predictive theories for systems from electronic to any observable scales as reviewed in the present work.
-
more » « less
Abstract Entropy and Information are key concepts not only in Information Theory but also in Physics: historically in the fields of Thermodynamics, Statistical and Analytical Mechanics, and, more recently, in the field of Information Physics. In this paper we argue that Information Physics reconciles and generalizes statistical, geometric, and mechanistic views on information. We start by demonstrating how the use and interpretation of Entropy and Information coincide in Information Theory, Statistical Thermodynamics, and Analytical Mechanics, and how this can be taken advantage of when addressing Earth Science problems in general and hydrological problems in particular. In the second part we discuss how Information Physics provides ways to quantify Information and Entropy from fundamental physical principles. This extends their use to cases where the preconditions to calculate Entropy in the classical manner as an aggregate statistical measure are not met. Indeed, these preconditions are rarely met in the Earth Sciences due either to limited observations or the far‐from‐equilibrium nature of evolving systems. Information Physics therefore offers new opportunities for improving the treatment of Earth Science problems.
-
Sharma, Pradeep (Ed.)Far-from-equilibrium phenomena are critical to all natural and engineered systems, and essential to biological processes responsible for life. For over a century and a half, since Carnot, Clausius, Maxwell, Boltzmann, and Gibbs, among many others, laid the foundation for our understanding of equilibrium processes, scientists and engineers have dreamed of an analogous treatment of nonequilibrium systems. But despite tremendous efforts, a universal theory of nonequilibrium behavior akin to equilibrium statistical mechanics and thermodynamics has evaded description. Several methodologies have proved their ability to accurately describe complex nonequilibrium systems at the macroscopic scale, but their accuracy and predictive capacity is predicated on either phenomenological kinetic equations fit to microscopic data or on running concurrent simulations at the particle level. Instead, we provide a novel framework for deriving stand-alone macroscopic thermodynamic models directly from microscopic physics without fitting in overdamped Langevin systems. The only necessary ingredient is a functional form for a parameterized, approximate density of states, in analogy to the assumption of a uniform density of states in the equilibrium microcanonical ensemble. We highlight this framework’s effectiveness by deriving analytical approximations for evolving mechanical and thermodynamic quantities in a model of coiled-coil proteins and double-stranded DNA, thus producing, to the authors’ knowledge, the first derivation of the governing equations for a phase propagating system under general loading conditions without appeal to phenomenology. The generality of our treatment allows for application to any system described by Langevin dynamics with arbitrary interaction energies and external driving, including colloidal macromolecules, hydrogels, and biopolymers.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1088/1751-8121/ac798a
