A Unified Picture of Adsorption on Transition Metals through Different Atoms
A key issue in catalyst design is understanding how adsorption energies of surface intermediates vary across both different surfaces and various types of adsorbing atoms. In this work, we examine trends in adsorption energies of a wide variety of adsorbates that attach to transition metal surfaces through different atoms (H, C, N, O, F, S, etc.). All adsorption energies, as calculated by density functional theory, have nearly identical dependence on the metal bands (the d-band center and the number of p electrons) and the adsorbates’ highest occupied molecular orbital (HOMO) energies. However, the dependence on the adsorbate-surface coupling and the d-band filling varies with the energy of the HOMO. Adsorbates with low HOMOs experience a higher level of Pauli repulsion than those with higher HOMOs. This leads to a classification of adsorbates into two groups, where adsorption energies in each group correlate. Even across the groups, adsorbates with similar HOMO energies are likely to have correlated adsorption energies.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1222130
- Journal Information:
- Journal of the American Chemical Society, 136(26):9272−9275, Journal Name: Journal of the American Chemical Society, 136(26):9272−9275
- Country of Publication:
- United States
- Language:
- English
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