Development and validation of reaxff reactive force field for hydrocarbon chemistry catalyzed by nickel

Jonathan E. Mueller, Adri Van Duin, William A. Goddard

Research output: Contribution to journalArticle

164 Citations (Scopus)

Abstract

To enable the study of hydrocarbon reactions catalyzed by nickel surfaces and particles using reactive molecular dynamics on thousands of atoms as a function of temperature and pressure, we have developed the ReaxFF reactive force field to describe adsorption, decomposition, reformation and desorption of hydrocarbons as they interact with the nickel surface. The ReaxFF parameters were determined by fitting to the geometries and energy surfaces from quantum mechanics (QM) calculations for a large number of reaction pathways for hydrocarbon molecules chemisorbed onto nickel (111), (100) and (110) surfaces, supplemented with QM equations of state for nickel and nickel carbides. We demonstrate the validity and accuracy of ReaxFF by applying it to study the reaction dynamics of hydrocarbons as catalyzed by nickel particles and surfaces. For the dissociation of methyl on the (111), (100), and stepped (111) surfaces of nickel, we observe the formation of chemisorbed CH plus subsurface carbide. We observe that the (111) surface is the least reactive, the (100) surface has the fastest reaction rates, and the stepped (111) surface has an intermediate reaction rate. The importance of surface defects in accelerating reaction rates is highlighted by these results.

Original languageEnglish (US)
Pages (from-to)4939-4949
Number of pages11
JournalJournal of Physical Chemistry C
Volume114
Issue number11
DOIs
StatePublished - Mar 25 2010

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Hydrocarbons
Nickel
field theory (physics)
hydrocarbons
nickel
chemistry
Reaction rates
reaction kinetics
Quantum theory
carbides
Carbides
quantum mechanics
surface geometry
Surface defects
surface defects
Equations of state
Interfacial energy
surface energy
Molecular dynamics
Desorption

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

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Development and validation of reaxff reactive force field for hydrocarbon chemistry catalyzed by nickel. / Mueller, Jonathan E.; Van Duin, Adri; Goddard, William A.

In: Journal of Physical Chemistry C, Vol. 114, No. 11, 25.03.2010, p. 4939-4949.

Research output: Contribution to journalArticle

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