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Fluctuations and bistability in a "hybrid" atomistic model for CO oxidation on nanofacets: An effective potential analysis

J. Chem. Phys. 117, 7319 (2002); doi:10.1063/1.1507105

Issue Date: 15 October 2002

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Da-Jiang Liu and J. W. Evans
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011
We analyze fluctuations in a "hybrid" atomistic model mimicking CO oxidation on nanoscale facets of metal(100) catalyst surfaces. The model incorporates a mean-field-like treatment of infinitely mobile CO, and a lattice-gas treatment of the superlattice ordering of immobile O. For an infinite system, it exhibits an Ising-type order–disorder transition for O, together with mean-field-like bistability disappearing at a cusp bifurcation. For finite systems, we use kinetic Monte Carlo simulation to study the probability distribution for the population of adsorbed species, from which bistability can be observed, together with fluctuation-induced transitions between the two stable states. An effective potential picture emerges from our analyses that can be used to quantify both the system size dependence of fluctuations and the transition rates. Thus, our hybrid atomistic model displays fluctuation behavior analogous to traditional mean-field models. This qualitative behavior can be understood by approximate treatments of population dynamics using master equations and Fokker–Planck equations. A generalized model with finite mobility of CO is also analyzed for comparison with the hybrid model. In contrast, it exhibits fluctuation behavior akin to equilibrium systems with Ising-type first-order transitions. ©2002 American Institute of Physics.
History: Received 12 April 2002; accepted 24 July 2002
Permalink: http://link.aip.org/link/?JCPSA6/117/7319/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.65.+r
    Physical chemistry and chemical physics Surface and interface chemistry; heterogeneous catalysis at surfaces (for temporal and spatial patterns in surface reactions, see 82.40.Np)
  • 82.40.Bj
    Physical chemistry and chemical physics Chemical kinetics and reactions: special regimes and techniques Oscillations, chaos, and bifurcations
  • 82.20.Kh
    Physical chemistry and chemical physics Chemical kinetics and dynamics Potential energy surfaces for chemical reactions
  • 82.20.Uv
    Physical chemistry and chemical physics Chemical kinetics and dynamics Stochastic theories of rate constants
  • YEAR: 2002

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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