A statistical mechanics framework for constructing nonequilibrium thermodynamic models

被引:4
|
作者
Leadbetter, Travis [1 ]
Purohit, Prashant K. [2 ]
Reina, Celia [2 ]
机构
[1] Univ Penn, Grad Grp Appl Math & Computat Sci, Philadelphia, PA 19104 USA
[2] Univ Penn, Dept Mech Engn & Appl Mech, Philadelphia, PA 19104 USA
来源
PNAS NEXUS | 2023年 / 2卷 / 12期
关键词
thermodynamics with internal variables; stochastic thermodynamics; variational approximation; PURE ICE-IV; THERMAL-PROPERTIES; WATER; XII; DYNAMICS; PHASE; DIFFRACTION; TRANSITION; ENTROPY; CREEP;
D O I
10.1093/pnasnexus/pgad417
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
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页数:10
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