There are known errors in oxidation energies of transition metal oxides caused by an improper treatment of their d-electrons. The Hubbard U is the cornputationally cheapest addition one can use to capture correct reaction energies, but the specific Hubbard U oftentimes m-uSt.be empirically determined only when suitable experimental data exist. We evaluated the effect of addling a calculated, linear response U on the predicted adsorption energies, scaling relationships, and activity trends with respect to the oxygen evolution reaction for a set of transition metal dioxides. We find that applying a U greater than zero always causes adsorption energies to be more endothermic. Furthermore, the addition of the Hubbard U greater than zero does not break scaling relationships established without the Hubbard U. The addition of the calculated linear response U value produces shifts of different systems along the activity volcano that results in improved activity trends when compared with experimental results.
- DENSITY-FUNCTIONAL THEORY
- WATER OXIDATION
- OXIDE SURFACES
Xu, Z., Rossmeisl, J., & Kitchin, J. R. (2015). A Linear Response DFT+U Study of Trends in the Oxygen Evolution Activity of Transition Metal Rutile Dioxides. The Journal of Physical Chemistry Part C, 119(9), 4827-4833. https://doi.org/10.1021/jp511426q