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Density-Dependent Liquid Nitromethane Decomposition: Molecular Dynamics Simulations Based on ReaxFF

Rom, Naomi and Zybin, Sergey V. and van Duin, Adri C. T. and Goddard, William A., III and Zeiri, Yehuda and Katz, Gil and Kosloff, Ronnie (2011) Density-Dependent Liquid Nitromethane Decomposition: Molecular Dynamics Simulations Based on ReaxFF. Journal of Physical Chemistry A, 115 (36). pp. 10181-10202. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20110927-123103516

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Abstract

The decomposition mechanism of hot liquid nitromethane at various compressions was studied using reactive force field (ReaxFF) molecular dynamics simulations. A competition between two different initial thermal decomposition schemes is observed, depending on compression. At low densities, unimolecular C–N bond cleavage is the dominant route, producing CH_3 and NO_2 fragments. As density and pressure rise approaching the Chapman–Jouget detonation conditions (~30% compression, >2500 K) the dominant mechanism switches to the formation of the CH_(3)NO fragment via H-transfer and/or N–O bond rupture. The change in the decomposition mechanism of hot liquid NM leads to a different kinetic and energetic behavior, as well as products distribution. The calculated density dependence of the enthalpy change correlates with the change in initial decomposition reaction mechanism. It can be used as a convenient and useful global parameter for the detection of reaction dynamics. Atomic averaged local diffusion coefficients are shown to be sensitive to the reactions dynamics, and can be used to distinguish between time periods where chemical reactions occur and diffusion-dominated, nonreactive time periods.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp202059vDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp202059vPublisherArticle
ORCID:
AuthorORCID
van Duin, Adri C. T.0000-0002-3478-4945
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2011 American Chemical Society. Published In Issue September 15, 2011; Article ASAP August 24, 2011; Just Accepted Manuscript: August 03, 2011; Received: March 03, 2011; Revised: July 20, 2011. This article posted ASAP on August 24, 2011. The 8th equation beneath Table 6 on page 10195 has been revised. The correct version posted on September 8, 2011. S.V.Z. and W.A.G. were supported by ARO (MURI-W911NF-05-1-0345) and ONR (N00014-05-1-0778, N00014-09-1-0634). Simulations were performed at DOD Major Shared Resource Centers under a DoD/HPCMP Challenge award (ARO-N27203C3K). R.K. and Y.Z. acknowledge support of The Center of Excellence for Explosives Detection, Mitigation and Response, Department of Homeland Security.
Funders:
Funding AgencyGrant Number
Army Research Office (ARO)W911NF-05-1-0345
Office of Naval Research (ONR)N00014-05-1-0778
Office of Naval Research (ONR)N00014-09-1-0634
Army Research Office (ARO)ARO-N27203C3K
Center of Excellence for Explosives Detection, Mitigation and Response, Department of Homeland SecurityUNSPECIFIED
Issue or Number:36
Record Number:CaltechAUTHORS:20110927-123103516
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110927-123103516
Official Citation:Density-Dependent Liquid Nitromethane Decomposition: Molecular Dynamics Simulations Based on ReaxFF Naomi Rom, Sergey V. Zybin, Adri C. T. van Duin, William A. Goddard III, Yehuda Zeiri, Gil Katz and, Ronnie Kosloff The Journal of Physical Chemistry A 2011 115 (36), 10181-10202
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:25448
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:28 Sep 2011 20:06
Last Modified:03 Oct 2019 03:06

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