Experiment-Based Kinetic Monte Carlo Simulations: CO Oxidation over RuO<sub>2</sub>(110)

Farkas, Attila; Heß, Franziska; Over, Herbert

doi:10.1021/jp204703p

Cited by 50 publications

(110 citation statements)

References 41 publications

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“…This implies that, a pressure of 4·10 −6 mbar would be necessary to achieve θ(CO ot ) = 1 if θ(CO ot ) = 0.5 at T = 350 K and p 1 = 10 −7 mbar. This result is roughly reconciled with the simulation results using our experiment-based kMC parameter set [83].…”

Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimsupporting

confidence: 80%

“…The first three have similar activation energies of about 75 to 90 kJ/mol. The activation energy for the fourth process is significantly higher with 125 kJ/mol [81][82][83].…”

Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimmentioning

confidence: 99%

“…Lateral interactions can be determined by DFT calculations or estimated from experiments, e.g., by fitting thermal desorption spectra or microcalorimetric measurements [91,92]. Recently, an experiment-based kMC approach has been developed and applied to the CO oxidation on RuO 2 (110) [83]. The guiding principle in obtaining a consistent set of input parameters for the experiment-based kMC simulations was to use dedicated temperature programmed reaction and desorption experiments (TPR, TPD) for each of the elementary reaction steps of the proposed reaction mechanism by starting from a well-defined coadsorbate surface configuration.…”

Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimmentioning

confidence: 99%

See 2 more Smart Citations

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

et al. 2015

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Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimsupporting

confidence: 80%

“…The first three have similar activation energies of about 75 to 90 kJ/mol. The activation energy for the fourth process is significantly higher with 125 kJ/mol [81][82][83].…”

Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimmentioning

confidence: 99%

Section: Kinetic Monte Carlo Simulations As a Tool To Connect Experimmentioning

confidence: 99%

See 1 more Smart Citation

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

et al. 2015

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“…It is common practice, usually employed in the implementations 9,18,23 of M-I, to assume that q ′ and q 0 ′ are equal to unity for the molecules and atoms adsorbed to the surface, or in transition states corresponding to on-surface diffusion. In our case, to reach a better accuracy, we calculate explicitly the vibrational frequencies of the adsorbates in O 2 ** and O* states, as well as in the dissociation transition state of the elementary reaction O 2 ** ⇄ 2O*, and use these data to calculate all partition functions in our M-II model (check the Supporting Information for details).…”

Section: Model and Methodsmentioning

confidence: 99%

A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO₂(110) Surface

Pogodin

López

2014

ACS Catal.

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The theoretical study of catalysis would substantialy benefit from the use of atomistic simulations that can provide information beyond mean-field approaches. To date, the nanoscale understanding of surface reactions has been only qualitatively achieved by means of kinetic Monte Carlo coupled to density functional theory, KMC-DFT. Here, we examine a widely employed model for oxygen interaction with the RuO2(110) surface, a highly anisotropic system. Our analysis reveals several covert problems that render as questionable the model’s predictions. We suggest an advanced approach that considers all the relevant elementary steps and configurations while smoothing the intrinsic errors in the DFT description of oxygen. Under these conditions, KMC provides quantitative agreement to temperature-programmed desorption experiments. These results illustrate how KMC-based simulations can be pushed forward so that they evolve toward being the standard methodology to study complex chemistry at the nanoscale.

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“…With the help of Grand canonical Monte Carlo (GCMC) and KMC simulations, it has become possible for the first time to explicitly study the effect of lateral interactions and adsorbate layer ordering on the kinetics of surface reactions . It has been thus shown that lateral interactions can have a dramatic influence on the reaction rate (several orders of magnitude), microkinetic reaction parameters (apparent activation energies and reaction orders), and even the relative catalytic activity of different crystal facets .…”

Section: Introductionmentioning

confidence: 99%

Efficient Implementation of Cluster Expansion Models in Surface Kinetic Monte Carlo Simulations with Lateral Interactions: Subtraction Schemes, Supersites, and the Supercluster Contraction

Heß

2019

J Comput Chem

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While lateral interaction models for reactions at surfaces have steadily gained popularity and grown in terms of complexity, their use in chemical kinetics has been impeded by the low performance of current kinetic Monte Carlo (KMC) algorithms. The origins of the additional computational cost in KMC simulations with lateral interactions are traced back to the more elaborate cluster expansion Hamiltonian, the more extensive rate updating, and to the impracticality of rate‐catalog‐based algorithms for interacting adsorbate systems. Favoring instead site‐based algorithms, we propose three ways to reduce the cost of KMC simulations: (1) representing the lattice energy by a smaller Supercluster Hamiltonian without loss of accuracy, (2) employing the subtraction schemes for updating key quantities in the simulation that undergo only small, local changes during a reaction event, and (3) applying efficient search algorithms from a set of established methods (supersite approach). The cost of the resulting algorithm is fixed with respect to the number of lattice sites for practical lattice sizes and scales with the square of the range of lateral interactions. The overall added cost of including a complex lateral interaction model amounts to less than a factor 3. Practical issues in implementation due to finite numerical accuracy are discussed in detail, and further suggestions for treating long‐range lateral interactions are made. We conclude that, while KMC simulations with complex lateral interaction models are challenging, these challenges can be overcome by modifying the established variable step‐size method by employing the supercluster, subtraction, and supersite algorithms (SSS‐VSSM). © 2019 Wiley Periodicals, Inc.

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Experiment-Based Kinetic Monte Carlo Simulations: CO Oxidation over RuO₂(110)

Cited by 50 publications

References 41 publications

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO₂(110) Surface

Efficient Implementation of Cluster Expansion Models in Surface Kinetic Monte Carlo Simulations with Lateral Interactions: Subtraction Schemes, Supersites, and the Supercluster Contraction

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Experiment-Based Kinetic Monte Carlo Simulations: CO Oxidation over RuO2(110)

Cited by 50 publications

References 41 publications

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

Combined experiment and theory approach in surface chemistry: Stairway to heaven?

A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO2(110) Surface

Efficient Implementation of Cluster Expansion Models in Surface Kinetic Monte Carlo Simulations with Lateral Interactions: Subtraction Schemes, Supersites, and the Supercluster Contraction

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Product

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Experiment-Based Kinetic Monte Carlo Simulations: CO Oxidation over RuO₂(110)

A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO₂(110) Surface