First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors
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Van Voorhis_First-Principles Monte.pdf
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Author(s)
Fetisov, Evgenii O.
Kuo, I-Feng William
Knight, Chris
VandeVondele, Joost
Van Voorhis, Troy
Siepmann, J. Ilja
Date Issued
June 2016
Journal
ACS Central Science
Publisher
American Chemical Society (ACS)
Citation
.Fetisov, Evgenii O. et al. “First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors.” ACS Central Science 2.6 (2016): 409–415. © 2016 American Chemical Society
Version
Final published version
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[subscript 2] and N[subscript 2]O in mole fractions approaching 1%, whereas N[subscript 3] and O[subscript 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acscentsci.6b00095
