Abstract
A new model of bonding between radical adsorbates and lattice oxygens is proposed that considers both the adsorbate-oxygen bonding and the weakening of the metal-oxygen bonds. Density functional calculations of SrMO3 perovskites for M being 3d, 4d, and 5d transition metals are used to correlate the bulk electronic structure with the surface-oxygen reactivity. Occupation of the metal-oxygen antibonding states, examined via the crystal orbital Hamilton population (COHP), is found to be a useful bulk descriptor that correlates with the vacancy formation energy of the lattice oxygen and its hydrogen adsorption energy. Analysis of density-of-states and COHP indicates that H adsorption energy is a combined result of formation of the O-H bond and the weakening of the surface metal-oxygen bond due to occupation of the metal-oxygen antibonding states by the electron from H. This insight will be useful in understanding the trends in surface reactivity of perovskites and transition-metal oxides in general.
| Original language | English |
|---|---|
| Pages (from-to) | 6321-6325 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 9 |
| Issue number | 21 |
| DOIs | |
| State | Published - Nov 1 2018 |
Funding
This research is sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
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