Molecular dynamics simulation of O2 sticking on Pt(111) using the ab initio based ReaxFF reactive force field

Paolo Valentini, Thomas E. Schwartzentruber, Ioana Cozmuta

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Abstract

The molecular dynamics technique with the ab initio based classical reactive force field ReaxFF is used to study the adsorption dynamics of O 2 on Pt(111) for both normal and oblique impacts. Overall, good quantitative agreement with the experimental data is found at low incident energies. Specifically, our simulations reproduce the characteristic minimum of the trapping probability at kinetic incident energies around 0.1 eV. This feature is determined by the presence of a physisorption well in the ReaxFF potential energy surface (PES) and the progressive suppression of a steering mechanism when increasing the translational kinetic energy (or the molecule's rotational energy) because of steric hindrance. In the energy range between 0.1 and 0.4 eV, the sticking probability increases, similar to molecular beam sticking data. For very energetic impacts (above 0.4 eV), ReaxFF predicts sticking probabilities lower than experimental sticking data by almost a factor of 3 due to an overall less attractive ReaxFF PES compared to experiments and density functional theory. For oblique impacts, the trapping probability is reduced by the nonzero parallel momentum because of the PES corrugation and does not scale with the total incident kinetic energy. Furthermore, our simulations predict quasispecular (slightly supraspecular) distributions of angles of reflection, in accordance with molecular beam experiments. Increasing the beam energy (between 1.2 and 1.7 eV) causes the angular distributions to broaden and to exhibit a tail toward the surface normal because molecules have enough momentum to get very near the surface and thus probe more corrugated repulsive regions of the PES.

Original languageEnglish (US)
Article number084703
JournalJournal of Chemical Physics
Volume133
Issue number8
DOIs
StatePublished - Aug 28 2010

Bibliographical note

Funding Information:
We would like to thank Professor Adri van Duin for his help with the ReaxFF potential and for providing us with the parameters for simulating the system of interest. The research was supported by the Air Force Office of Scientific Research (AFOSR) under Grant Nos. FA9550-04-1-0341 and FA9550-09-1-0157. The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily representing the official policies or endorsements, either expressed or implied, of the AFOSR or the U.S. Government. P.V. would like to acknowledge partial support from the Doctoral Dissertation Fellowship of the University of Minnesota. A portion of the funding for the work of Dr. Ioana Cozmuta originates from NASA's Fundamental Aeronautics Hypersonic Program under the ELORET contract NNA04BC25C.

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