A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO2(110) SurfaceClick to copy article linkArticle link copied!
Abstract
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.
1 Introduction
Figure 1
Figure 1. Schematic illustration of a RuO2(110) surface and of its representation as a KMC simulation lattice. The dashed rectangle shows the unit cell’s size. Under normal conditions, all the bridge sites are occupied by oxygen atoms.
Figure 2
Figure 2. Energy levels of O2 on a RuO2(110) surface (center), calculated for various configurations of molecular (O2, O2*, O2**) and atomic (O*) oxygen, illustrated in the bottom. All the values are given in eV. The black profile shows the actual output of DFT, and the red one corresponds to an empirically corrected one (more details in the text). The energies for O2* and 2O* configurations split into several levels (α, β, γ) for different oxygen coverages of the neighboring surface sites are shown on the left of the illustration (the red frames show the targeted adsorption sites). Finally, the one-step profile at the right corresponds to the oxygen adsorption and desorption representation in ref 18.
2 Model and Methods


Figure 3
Figure 3. Temperature dependences (on top) of the rates of elementary reactions involved in oxygen adsorption to RuO2(110): O2 → O2** (solid blue for p = 1 bar, dashed blue for p = 10–10 bar); O2** → O2 (red); O2** → 2O* (green); 2O* → O2** (oxygen association, thin black). The thick black line shows the oxygen desorption rate according to our M-I model. The bottom plot shows the absolute deviation of the black thick line from the thin solid black one.
3 Results and Discussion
Figure 4
Figure 4. O2 TPD profile of oxygen in 350–550 K range of temperatures. Experimental (22) data (dashed) are shown alongside with results obtained by KMC simulations in ref 18 (thick black) and by our own KMC simulations with use of the model described in the present work (thin black line). The red line shows a special postprocessing, explained in the text, of our simulation results, that shows a perfect match with the experimental measurements. All the peaks are normalized for the same area.
Figure 5
Figure 5. Rates of O2** → O2 (red) and 2O* → O2** (black) reactions, calculated according to our implementation of the M-II model (solid) are compared with the approximate values obtained with partition functions of adsorbed molecules and atoms set to unity (dashed) or with energy barrier value modified by ±0.1 eV (dotted). The bottom plot shows the absolute deviations of the approximate lines from the original ones.

4 Conclusions
Supporting Information
A summary with the detailed models. This material is available free of charge via the Internet at http://pubs.acs.org/.
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgment
This work has been supported through the ERC-2010-StG-258406, and we are grateful for the generous computing resources from BSC-RES. We also thank Dr. D. Teschner for useful discussions.
References
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Abstract
Figure 1
Figure 1. Schematic illustration of a RuO2(110) surface and of its representation as a KMC simulation lattice. The dashed rectangle shows the unit cell’s size. Under normal conditions, all the bridge sites are occupied by oxygen atoms.
Figure 2
Figure 2. Energy levels of O2 on a RuO2(110) surface (center), calculated for various configurations of molecular (O2, O2*, O2**) and atomic (O*) oxygen, illustrated in the bottom. All the values are given in eV. The black profile shows the actual output of DFT, and the red one corresponds to an empirically corrected one (more details in the text). The energies for O2* and 2O* configurations split into several levels (α, β, γ) for different oxygen coverages of the neighboring surface sites are shown on the left of the illustration (the red frames show the targeted adsorption sites). Finally, the one-step profile at the right corresponds to the oxygen adsorption and desorption representation in ref 18.
Figure 3
Figure 3. Temperature dependences (on top) of the rates of elementary reactions involved in oxygen adsorption to RuO2(110): O2 → O2** (solid blue for p = 1 bar, dashed blue for p = 10–10 bar); O2** → O2 (red); O2** → 2O* (green); 2O* → O2** (oxygen association, thin black). The thick black line shows the oxygen desorption rate according to our M-I model. The bottom plot shows the absolute deviation of the black thick line from the thin solid black one.
Figure 4
Figure 4. O2 TPD profile of oxygen in 350–550 K range of temperatures. Experimental (22) data (dashed) are shown alongside with results obtained by KMC simulations in ref 18 (thick black) and by our own KMC simulations with use of the model described in the present work (thin black line). The red line shows a special postprocessing, explained in the text, of our simulation results, that shows a perfect match with the experimental measurements. All the peaks are normalized for the same area.
Figure 5
Figure 5. Rates of O2** → O2 (red) and 2O* → O2** (black) reactions, calculated according to our implementation of the M-II model (solid) are compared with the approximate values obtained with partition functions of adsorbed molecules and atoms set to unity (dashed) or with energy barrier value modified by ±0.1 eV (dotted). The bottom plot shows the absolute deviations of the approximate lines from the original ones.
References
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