Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory

Francis, Michael Frederick

doi:10.1021/acs.jpca.8b06238

Title: Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory

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Abstract

A broad class of reaction networks are controlled not by any thermodynamic ensemble but by rates and are referred to as “kinetically constrained”. Here in this paper, microkinetic rate theory is extended into a model of arbitrarily complex reaction networks. This microkinetic rate theory takes a form where the constraints imposed by kinetically constrained systems apply naturally. This model is compared to numerically complete results and is shown to be quantitatively predictive. Model deviations are shown to emerge for systems with incomplete mixing. Finally, this model is analytical and may serve as a basis for device and continuum scale rate modeling.

Authors:

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: Fri Sep 07 00:00:00 EDT 2018

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Laboratory Directed Research and Development (LDRD) Program

OSTI Identifier:: 1477649

Report Number(s):: LA-UR-17-29795
Journal ID: ISSN 1089-5639

Grant/Contract Number:: AC52-06NA25396

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 122; Journal Issue: 37; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING; Energy Sciences; Mathematics; Material Science

Citation Formats


                    Francis, Michael Frederick. Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpca.8b06238.

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                    Francis, Michael Frederick. Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory.  United States.  https://doi.org/10.1021/acs.jpca.8b06238

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                    Francis, Michael Frederick. Fri .  
"Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory".  United States.  https://doi.org/10.1021/acs.jpca.8b06238.  https://www.osti.gov/servlets/purl/1477649.

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@article{osti_1477649,

  title        = {Continuum Microkinetic Rate Theory of Lattice Systems: Formalization, Current Limitations, and a Possible Basis for Continuum Rate Theory},

  author       = {Francis, Michael Frederick},

  abstractNote = {A broad class of reaction networks are controlled not by any thermodynamic ensemble but by rates and are referred to as “kinetically constrained”. Here in this paper, microkinetic rate theory is extended into a model of arbitrarily complex reaction networks. This microkinetic rate theory takes a form where the constraints imposed by kinetically constrained systems apply naturally. This model is compared to numerically complete results and is shown to be quantitatively predictive. Model deviations are shown to emerge for systems with incomplete mixing. Finally, this model is analytical and may serve as a basis for device and continuum scale rate modeling.},

  doi          = {10.1021/acs.jpca.8b06238},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 37,

  volume       = 122,

  place        = {United States},

  year         = {Fri Sep 07 00:00:00 EDT 2018},

  month        = {Fri Sep 07 00:00:00 EDT 2018}

}

Copy to clipboard

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