title: First-Principles Free-Energy Barriers for Photoelectrochemical Surface Reactions: Proton Abstraction at TiO_{2}(110).
abstract: We explicitly calculate the free-energy barrier for the initial proton abstraction in the water splitting reaction at rutile TiO_{2}(110) through ab initio molecular dynamics. Combining solid-state embedding, an energy based reaction coordinate and state-of-the-art free-energy reconstruction techniques renders the calculation tractable at the hybrid density-functional theory level. The obtained free-energy barrier of approximately 0.2 eV, depending slightly on the orientation of the first acceptor water molecule, suggests a hindered reaction on the pristine rutile surface.
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Stecher
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter
authors.affiliation: Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
authors.forename: Harald
authors.initials: H
authors.lastname: Oberhofer