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First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors

[Image: see text] Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bo...

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Autores principales: Fetisov, Evgenii O., Kuo, I-Feng William, Knight, Chris, VandeVondele, Joost, Van Voorhis, Troy, Siepmann, J. Ilja
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2016
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4919768/
https://www.ncbi.nlm.nih.gov/pubmed/27413785
http://dx.doi.org/10.1021/acscentsci.6b00095
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author Fetisov, Evgenii O.
Kuo, I-Feng William
Knight, Chris
VandeVondele, Joost
Van Voorhis, Troy
Siepmann, J. Ilja
author_facet Fetisov, Evgenii O.
Kuo, I-Feng William
Knight, Chris
VandeVondele, Joost
Van Voorhis, Troy
Siepmann, J. Ilja
author_sort Fetisov, Evgenii O.
collection PubMed
description [Image: see text] Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gas equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO(2) and N(2)O in mole fractions approaching 1%, whereas N(3) and O(3) are not observed. The equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.
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spelling pubmed-49197682016-07-13 First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors Fetisov, Evgenii O. Kuo, I-Feng William Knight, Chris VandeVondele, Joost Van Voorhis, Troy Siepmann, J. Ilja ACS Cent Sci [Image: see text] Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gas equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO(2) and N(2)O in mole fractions approaching 1%, whereas N(3) and O(3) are not observed. The equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data. American Chemical Society 2016-06-13 2016-06-22 /pmc/articles/PMC4919768/ /pubmed/27413785 http://dx.doi.org/10.1021/acscentsci.6b00095 Text en Copyright © 2016 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Fetisov, Evgenii O.
Kuo, I-Feng William
Knight, Chris
VandeVondele, Joost
Van Voorhis, Troy
Siepmann, J. Ilja
First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title_full First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title_fullStr First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title_full_unstemmed First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title_short First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
title_sort first-principles monte carlo simulations of reaction equilibria in compressed vapors
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4919768/
https://www.ncbi.nlm.nih.gov/pubmed/27413785
http://dx.doi.org/10.1021/acscentsci.6b00095
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