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Accurate Surface Chemistry beyond the Generalized Gradient Approximation: Illustrations for Graphene Adatoms

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Department of Chemistry, Texas Christian University, Fort Worth, Texas 76129, United States
Department of Physics, Central Michigan University, Mt. Pleasant, Michigan 48859, United States
§ Chemistry Department, Texas A&M University at Qatar, Texas A&M Engineering Building, Education City, Doha, Qatar
Cite this: J. Chem. Theory Comput. 2013, 9, 11, 4853–4859
Publication Date (Web):October 21, 2013
Copyright © 2013 American Chemical Society

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    Simulations of surface chemistry often use density functional theory with generalized gradient approximations (GGAs) for the exchange-correlation functional. GGAs have well-known limitations for gas-phase chemistry, including underestimated reaction barriers, and are largely superseded by meta-GGAs and hybrids. Our simulations of O and Li adatoms on graphene add to a growing body of evidence that GGAs have similar limitations on surfaces and that meta-GGAs and screened hybrids are computationally feasible for such systems. Meta-GGAs and screened hybrids systematically improve accuracy, just as they do for gas-phase chemistry, motivating their continued exploration in surface chemistry.

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