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Title: First-principles Monte Carlo simulations of reaction equilibria in compressed vapors

Abstract

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 2O in mole fractions approaching 1%, whereas N 3 and O 3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from amore » thermochemical computer code parametrized to experimental data.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. ETH Zurich, Zurich (Switzerland)
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; Argonne National Laboratory - Argonne Leadership Computing Facility
OSTI Identifier:
1256780
Alternate Identifier(s):
OSTI ID: 1350690; OSTI ID: 1367967
Report Number(s):
LLNL-JRNL-686898
Journal ID: ISSN 2374-7943; 126865
Grant/Contract Number:  
AC02-06CH11357; AC52-07NA27344
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 2; Journal Issue: 6; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 97 MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE

Citation Formats

Fetisov, Evgenii O., Kuo, I-Feng William, Knight, Chris, VandeVondele, Joost, Van Voorhis, Troy, and Siepmann, J. Ilja. First-principles Monte Carlo simulations of reaction equilibria in compressed vapors. United States: N. p., 2016. Web. doi:10.1021/acscentsci.6b00095.
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. United States. doi:10.1021/acscentsci.6b00095.
Fetisov, Evgenii O., Kuo, I-Feng William, Knight, Chris, VandeVondele, Joost, Van Voorhis, Troy, and Siepmann, J. Ilja. Mon . "First-principles Monte Carlo simulations of reaction equilibria in compressed vapors". United States. doi:10.1021/acscentsci.6b00095.
@article{osti_1256780,
title = {First-principles Monte Carlo simulations of reaction equilibria in compressed vapors},
author = {Fetisov, Evgenii O. and Kuo, I-Feng William and Knight, Chris and VandeVondele, Joost and Van Voorhis, Troy and Siepmann, J. Ilja},
abstractNote = {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 NO2 and N2O in mole fractions approaching 1%, whereas N3 and O3 are not observed. Lastly, the equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.},
doi = {10.1021/acscentsci.6b00095},
journal = {ACS Central Science},
number = 6,
volume = 2,
place = {United States},
year = {Mon Jun 13 00:00:00 EDT 2016},
month = {Mon Jun 13 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acscentsci.6b00095

Citation Metrics:
Cited by: 3 works
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