ReaxFF reactive force field development and applications for molecular dynamics simulations of ammonia borane dehydrogenation and combustion

Michael R. Weismiller, Adri Van Duin, Jongguen Lee, Richard A. Yetter

Research output: Contribution to journalArticle

82 Citations (Scopus)

Abstract

Ammonia borane (AB) has attracted significant attention due to its high hydrogen content (19.6% by mass). To investigate the reaction mechanism associated with the combustion of AB, a reactive force field (ReaxFF) has been developed for use in molecular dynamics (MD) simulations. The ReaxFF parameters have been derived directly from quantum mechanical data (QM). NVT-MD simulations of single- and polymolecular AB thermolysis were conducted in order to validate the force field. The release of the first equivalent H2 is a unimolecular reaction, and MD simulations show an activation energy of 26.36 kcal mol'1, which is in good agreement with experimental results. The release of the second H2 is also a unimolecular reaction; however, the release of a third H2 requires the formation of a B'N polymer. Similar simulations were conducted with a boron and oxygen system, since the oxidation of boron will be an integral step in AB combustion, and show good agreement with the established mechanism for this system. At low temperatures, boron atoms agglomerate into a cluster, which is oxidized at higher temperatures, eventually forming condensed and gas phase boron'oxide-species. These MD results provide confidence that ReaxFF can properly model the oxidation of AB and provide mechanistic insight into the AB dehydrogation and combustion reactions.

Original languageEnglish (US)
Pages (from-to)5485-5492
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number17
DOIs
StatePublished - May 6 2010

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Boranes
boranes
Dehydrogenation
dehydrogenation
Ammonia
field theory (physics)
Molecular dynamics
ammonia
molecular dynamics
Boron
Computer simulation
boron
simulation
oxygen supply equipment
boron oxides
Oxidation
Thermolysis
oxidation
Hydrogen
confidence

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Ammonia borane (AB) has attracted significant attention due to its high hydrogen content (19.6{\%} by mass). To investigate the reaction mechanism associated with the combustion of AB, a reactive force field (ReaxFF) has been developed for use in molecular dynamics (MD) simulations. The ReaxFF parameters have been derived directly from quantum mechanical data (QM). NVT-MD simulations of single- and polymolecular AB thermolysis were conducted in order to validate the force field. The release of the first equivalent H2 is a unimolecular reaction, and MD simulations show an activation energy of 26.36 kcal mol'1, which is in good agreement with experimental results. The release of the second H2 is also a unimolecular reaction; however, the release of a third H2 requires the formation of a B'N polymer. Similar simulations were conducted with a boron and oxygen system, since the oxidation of boron will be an integral step in AB combustion, and show good agreement with the established mechanism for this system. At low temperatures, boron atoms agglomerate into a cluster, which is oxidized at higher temperatures, eventually forming condensed and gas phase boron'oxide-species. These MD results provide confidence that ReaxFF can properly model the oxidation of AB and provide mechanistic insight into the AB dehydrogation and combustion reactions.",
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ReaxFF reactive force field development and applications for molecular dynamics simulations of ammonia borane dehydrogenation and combustion. / Weismiller, Michael R.; Van Duin, Adri; Lee, Jongguen; Yetter, Richard A.

In: Journal of Physical Chemistry A, Vol. 114, No. 17, 06.05.2010, p. 5485-5492.

Research output: Contribution to journalArticle

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