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Application of the ReaxFF Reactive Force Field to Reactive Dynamics of Hydrocarbon Chemisorption and Decomposition

Mueller, Jonathan E. and van Duin, Adri C. T. and Goddard, William A., III (2010) Application of the ReaxFF Reactive Force Field to Reactive Dynamics of Hydrocarbon Chemisorption and Decomposition. Journal of Physical Chemistry C, 114 (12). pp. 5675-5685. ISSN 1932-7447.

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We report here reactive dynamics (RD) simulations of the adsorption and decomposition of a gas of 20−120 methane, ethyne, ethene, benzene, cyclohexane, or propene molecules interacting with a 21 Å diameter nickel nanoparticle (468 atoms). These RD simulations use the recently developed ReaxFF reactive force field to describe decomposition, reactivity, and desorption of hydrocarbons as they interact with nickel surfaces. We carried out 100 ps of RD as the temperature is ramped at a constant rate from 500 to 2500 K (temperature programmed reactions). We find that all four unsaturated hydrocarbon species chemisorb to the catalyst particle with essentially no activation energy (attaching to the surface through π electrons) and then proceed to decompose by breaking C−H bonds to form partially dehydrogenated species prior to decomposition to lower order hydrocarbons. The eventual breaking of C−C bonds usually involves a surface Ni atom inserting into the C−C bond to produce an atomic C that simultaneously with C−C cleavage moves into the subsurface layer of the particle. The greater stability of this subsurface atomic C (forming up to four Ni−C bonds) over adatom C on the particle surface (forming at most three Ni−C bonds) is critical for favorable cleaving of C−C bonds. For the two saturated hydrocarbon species (methane and cyclohexane), we observe an activation energy associated with dissociative chemisorption. These results are consistent with available experimental reactivity data and quantum mechanics (QM) energy surfaces, validating the accuracy of ReaxFF for studying hydrocarbon decomposition on nickel clusters.

Item Type:Article
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URLURL TypeDescription
Mueller, Jonathan E.0000-0001-8811-8799
van Duin, Adri C. T.0000-0002-3478-4945
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2010 American Chemical Society. Published In Issue April 01, 2010. Article ASAP January 27, 2010. Received: September 14, 2009. Revised: December 16, 2009. Publication Date (Web): January 27, 2010. This research was supported partly by Intel Components Research and by Intel Corporate Research.
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Issue or Number:12
Record Number:CaltechAUTHORS:20100413-132736309
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Official Citation:Application of the ReaxFF Reactive Force Field to Reactive Dynamics of Hydrocarbon Chemisorption and Decomposition Jonathan E. Mueller, Adri C. T. van Duin, William A. Goddard III The Journal of Physical Chemistry C 2010 114 (12), 5675-5685
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:17962
Deposited By: Tony Diaz
Deposited On:28 Apr 2010 18:16
Last Modified:17 Nov 2020 00:56

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