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Title: Flat-Histogram Monte Carlo as an Efficient Tool To Evaluate Adsorption Processes Involving Rigid and Deformable Molecules

Abstract

Monte Carlo simulations are the foundational technique for predicting thermodynamic properties of open systems where the process of interest involves the exchange of particles. Thus, they have been used extensively to computationally evaluate the adsorption properties of nanoporous materials and are critical for the in silico identification of promising materials for a variety of gas storage and chemical separation applications. In this work we demonstrate that a well-known biasing technique, known as “flat-histogram” sampling, can be combined with temperature extrapolation of the free energy landscape to efficiently provide significantly more useful thermodynamic information than standard open ensemble MC simulations. Namely, we can accurately compute the isosteric heat of adsorption and number of particles adsorbed for various adsorbates over an extremely wide range of temperatures and pressures from a set of simulations at just one temperature. We extend this derivation of the temperature extrapolation to adsorbates with intramolecular degrees of freedom when Rosenbluth sampling is employed. Consequently, the working capacity and isosteric heat can be computed for any given combined temperature/pressure swing adsorption process for a large range of operating conditions with both rigid and deformable adsorbates. Finally, continuous thermodynamic properties can be computed with this technique at very moderate computationalmore » cost, thereby providing a strong case for its application to the in silico identification of promising nanoporous adsorbents.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Ecole Polytechnique Federale Lausanne (Switzlerland). Lab. of Molecular Simulation (LSMO), Inst. des Sciences et Ingénierie Chimiques
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566509
Grant/Contract Number:  
SC0001015
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Witman, Matthew, Mahynski, Nathan A., and Smit, Berend. Flat-Histogram Monte Carlo as an Efficient Tool To Evaluate Adsorption Processes Involving Rigid and Deformable Molecules. United States: N. p., 2018. Web. doi:10.1021/acs.jctc.8b00534.
Witman, Matthew, Mahynski, Nathan A., & Smit, Berend. Flat-Histogram Monte Carlo as an Efficient Tool To Evaluate Adsorption Processes Involving Rigid and Deformable Molecules. United States. doi:10.1021/acs.jctc.8b00534.
Witman, Matthew, Mahynski, Nathan A., and Smit, Berend. Mon . "Flat-Histogram Monte Carlo as an Efficient Tool To Evaluate Adsorption Processes Involving Rigid and Deformable Molecules". United States. doi:10.1021/acs.jctc.8b00534. https://www.osti.gov/servlets/purl/1566509.
@article{osti_1566509,
title = {Flat-Histogram Monte Carlo as an Efficient Tool To Evaluate Adsorption Processes Involving Rigid and Deformable Molecules},
author = {Witman, Matthew and Mahynski, Nathan A. and Smit, Berend},
abstractNote = {Monte Carlo simulations are the foundational technique for predicting thermodynamic properties of open systems where the process of interest involves the exchange of particles. Thus, they have been used extensively to computationally evaluate the adsorption properties of nanoporous materials and are critical for the in silico identification of promising materials for a variety of gas storage and chemical separation applications. In this work we demonstrate that a well-known biasing technique, known as “flat-histogram” sampling, can be combined with temperature extrapolation of the free energy landscape to efficiently provide significantly more useful thermodynamic information than standard open ensemble MC simulations. Namely, we can accurately compute the isosteric heat of adsorption and number of particles adsorbed for various adsorbates over an extremely wide range of temperatures and pressures from a set of simulations at just one temperature. We extend this derivation of the temperature extrapolation to adsorbates with intramolecular degrees of freedom when Rosenbluth sampling is employed. Consequently, the working capacity and isosteric heat can be computed for any given combined temperature/pressure swing adsorption process for a large range of operating conditions with both rigid and deformable adsorbates. Finally, continuous thermodynamic properties can be computed with this technique at very moderate computational cost, thereby providing a strong case for its application to the in silico identification of promising nanoporous adsorbents.},
doi = {10.1021/acs.jctc.8b00534},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 14,
place = {United States},
year = {2018},
month = {10}
}

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