Theoretical and Experimental Studies of the Reactions between Hyperthermal O(3P) and Graphite: Graphene-Based Direct Dynamics and Beam-Surface Scattering Approaches

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Abstract
Beam-surface scattering experiments and theoretical direct dynamics based on density functional theory calculations are used to investigate hyperthermal collisions between O(3P) and highly oriented pyrolytic graphite (HOPG). The simulations suggest that the HOPG surface becomes functionalized with epoxide groups. Intersystem crossing (ISC) between the lowest-energy triplet and singlet potential-energy surfaces is not necessary for this functionalization to occur. Both theory and experiment indicate that incoming O atoms can react at the surface to form O2 by way of an Eley−Rideal mechanism. They also suggest that the collisions can result in the production of CO and CO2 by way of both direct and complex reaction mechanisms. The direct dynamics simulations provide significant insight into the details of the complex reaction mechanisms. Semiquinones are present at defect sites and can form in functionalized pristine sheets, the latter resulting in the formation of a defect. Direct collision of an incoming O atom with a semiquinone or vibrational excitation caused by a nearby O-atom collision can cause the release of the semiquinone CO, forming carbon monoxide. The CO may react with an oxygen atom on the surface to become CO2 before receding from the surface. The simulations also illustrate how epoxide groups neighboring semiquinones catalyze the release of CO. Throughout, the experimental results are observed to be consistent with the theoretical calculations.

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