A Framework of Nonequilibrium Statistical Mechanics. II. Coarse-Graining
- For a given thermodynamic system, and a given choice of coarse-grained state variables, the knowledge of a force-flux constitutive law is the basis for any nonequilibrium modeling. In the first paper of this series we established how, by a generalization of the classical fluctuation-dissipation theorem (FDT), the structure of a constitutive law is directly related to the distribution of the fluctuations of the state variables. When these fluctuations can be expressed in terms of diffusion processes, one may use Green–Kubo-type coarse-graining schemes to find the constitutive laws. In this paper we propose a coarse-graining method that is valid when the fluctuations are described by means of general Markov processes, which include diffusions as a special case. We prove the success of the method by numerically computing the constitutive law for a simple chemical reaction A⇄B. Furthermore, we show that, for such a system, one cannot find a consistent constitutive law by any Green–Kubo-like scheme.
Author: | Alberto MontefuscoORCiD, Mark A. PeletierORCiD, Hans Christian ÖttingerORCiD |
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Document Type: | Article |
Parent Title (English): | Journal of Non-Equilibrium Thermodynamics |
Volume: | 46 |
Issue: | 1 |
First Page: | 15 |
Last Page: | 33 |
Publisher: | De Gruyter |
Year of first publication: | 2021 |
DOI: | https://doi.org/10.1515/jnet-2020-0069 |