CO oxidation reaction on Pt(111) studied by the dynamic Monte Carlo method including lateral interactions of adsorbates.

The dynamics of adsorbate structures during CO oxidation on Pt(111) surfaces and its effects on the reaction were studied by the dynamic Monte Carlo method including lateral interactions of adsorbates. The lateral interaction energies between adsorbed species were calculated by the density functional theory method. Dynamic Monte Carlo simulations were performed for the oxidation reaction over a mesoscopic scale, where the experimentally determined activation energies of elementary paths were altered by the calculated lateral interaction energies. The simulated results reproduced the characteristics of the microscopic and mesoscopic scale adsorbate structures formed during the reaction, and revealed that the complicated reaction kinetics is comprehensively explained by a single reaction path affected by the surrounding adsorbates. We also propose from the simulations that weakly adsorbed CO molecules at domain boundaries promote the island-periphery specific reaction.

[1]  G. Ertl,et al.  A molecular beam investigation of the interactions of CO with a Pt(111) surface , 1981 .

[2]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[3]  Alexander S. Mikhailov,et al.  Controlling Chemical Turbulence by Global Delayed Feedback: Pattern Formation in Catalytic CO Oxidation on Pt(110) , 2001, Science.

[4]  G. Ertl,et al.  Spatiotemporal Self-Organization in a Surface Reaction: From the Atomic to the Mesoscopic Scale , 2001, Science.

[5]  Ertl,et al.  Atomic and macroscopic reaction rates of a surface-catalyzed reaction , 1997, Science.

[6]  T. Nordmeyer,et al.  STICKING PROBABILITIES FOR CO ADSORPTION ON PT(111) SURFACES REVISITED , 1995 .

[7]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[8]  T. Arias,et al.  Iterative minimization techniques for ab initio total energy calculations: molecular dynamics and co , 1992 .

[9]  N. V. Petrova,et al.  Monte Carlo simulation of CO and O coadsorption and reaction on Pt(111) , 2005 .

[10]  Daan Frenkel,et al.  The steady state of heterogeneous catalysis, studied by first-principles statistical mechanics. , 2004, Physical review letters.

[11]  Paxton,et al.  High-precision sampling for Brillouin-zone integration in metals. , 1989, Physical review. B, Condensed matter.

[12]  H. Steinrück,et al.  Kinetic parameters of CO adsorbed on Pt(111) studied by in situ high resolution x-ray photoelectron spectroscopy , 2002 .

[13]  H. Steinrück,et al.  Adsorption and desorption of CO on Ru(0001): A comprehensive analysis , 2003 .

[14]  Jpl John Segers,et al.  Efficient Monte Carlo methods for the simulation of catalytic surface reactions , 1998 .

[15]  Ali Alavi,et al.  CO oxidation on Pt(111): An ab initio density functional theory study , 1998 .

[16]  M. Scheffler,et al.  First-Principles Theory of Surface Thermodynamics and Kinetics , 1999, cond-mat/9908213.

[17]  M. Kawai,et al.  Thermal excitation of oxygen species as a trigger for the CO oxidation on Pt(111) , 1995 .

[18]  R. Ferrando,et al.  Collective and single particle diffusion on surfaces , 2002 .

[19]  T. Ohta,et al.  Oxygen island formation on Pt(111) studied by dynamic Monte Carlo simulation. , 2005, The Journal of chemical physics.

[20]  G. Ertl,et al.  A molecular beam study of the catalytic oxidation of CO on a Pt(111) surface , 1980 .

[21]  Steffen Renisch,et al.  Real-time STM observations of atomic equilibrium fluctuations in an adsorbate system: O/Ru(0001) , 1997 .

[22]  A. Locatelli,et al.  Structural determination of molecules adsorbed in different sites by means of chemical shift photoelectron diffraction: c(4×2)-CO on Pt(111) , 2000 .

[23]  D. Vanderbilt,et al.  Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. , 1990, Physical review. B, Condensed matter.

[24]  D. Doren,et al.  CO diffusion on Pt(111) with time-resolved infrared-pulsed molecular beam methods : critical tests and analysis , 1990 .

[25]  G. Ertl,et al.  Imaging of spatio-temporal pattern evolution during carbon monoxide oxidation on platinum , 1990, Nature.

[26]  G. Kresse,et al.  Ab initio molecular dynamics for liquid metals. , 1993 .

[27]  J. Wintterlin,et al.  CO oxidation on Pt(111)—Scanning tunneling microscopy experiments and Monte Carlo simulations , 2001 .

[28]  F. Zaera,et al.  Isothermal study of the kinetics of carbon monoxide oxidation on Pt(111): Rate dependence on surface coverages , 1997 .

[29]  Irving Langmuir,et al.  The mechanism of the catalytic action of platinum in the reactions 2Co + O2= 2Co2 and 2H2+ O2= 2H2O , 1922 .

[30]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[31]  M. Hove,et al.  Reliability of detailed LEED structural analyses : Pt(111) and Pt(111)-p(2×2)-O , 1995 .

[32]  M. Silverberg,et al.  On the effects of adsorbate aggregation on the kinetics of surface reactions , 1985 .

[33]  Ertl,et al.  Existence of a 'Hot' Atom Mechanism for the Dissociation of O2 on Pt(111). , 1996, Physical review letters.

[34]  W. H. Weinberg,et al.  Theoretical foundations of dynamical Monte Carlo simulations , 1991 .

[35]  W. H. Weinberg,et al.  Dynamic Monte Carlo with a proper energy barrier: Surface diffusion and two‐dimensional domain ordering , 1989 .

[36]  T. Shimada,et al.  Mechanism of the CO oxidation reaction on O-precovered Pt(111) surfaces studied with near-edge x-ray absorption fine structure spectroscopy. , 2005, The Journal of chemical physics.

[37]  H. Steinrück,et al.  Kinetics of the CO oxidation reaction on Pt(111) studied by in situ high-resolution x-ray photoelectron spectroscopy. , 2004, The Journal of chemical physics.