Stecher Thomas, Reuter Karsten, Oberhofer Harald
Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
Phys Rev Lett. 2016 Dec 30;117(27):276001. doi: 10.1103/PhysRevLett.117.276001. Epub 2016 Dec 29.
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.
我们通过从头算分子动力学明确计算了金红石型TiO₂(110)水分解反应中初始质子抽取的自由能垒。结合固态嵌入、基于能量的反应坐标和最先进的自由能重构技术，使得在杂化密度泛函理论水平上的计算变得可行。所获得的约0.2 eV的自由能垒，略取决于第一个受体水分子的取向，这表明在原始金红石表面上反应受到阻碍。
