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Bulk and surface contributions to ionisation potentials of metal oxides

Zhang, Xingfan, Liu, Taifeng, Zhu, Lei, Guan, Jingcheng, Lu, You, Keal, Thomas W., Buckeridge, John, Catlow, C. Richard A. ORCID: and Sokol, Alexey A. 2023. Bulk and surface contributions to ionisation potentials of metal oxides. Angewandte Chemie 135 (40) , e202308411. 10.1002/ange.202308411

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Determining the absolute band edge positions in solid materials is crucial for optimising their performance in wide‐ranging applications including photocatalysis and electronic devices. However, obtaining absolute energies is challenging, as seen in CeO2, where experimental measurements show substantial discrepancies in the ionisation potential (IP). Here, we have combined several theoretical approaches, from classical electrostatics to quantum mechanics, to elucidate the bulk and surface contributions to the IP of metal oxides. We have determined a theoretical bulk contribution to the IP of stoichiometric CeO2 of only 5.38 eV, while surface orientation results in intrinsic IP variations ranging from 4.2 eV to 8.2 eV. Highly tuneable IPs were also found in TiO2, ZrO2, and HfO2, in which surface polarisation plays a pivotal role in long‐range energy level shifting. Our analysis, in addition to rationalising the observed range of experimental results, provides a firm basis for future interpretations of experimental and computational studies of oxide band structures.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Additional Information: License information from Publisher: LICENSE 1: URL:
Publisher: Wiley
ISSN: 0044-8249
Date of First Compliant Deposit: 25 August 2023
Date of Acceptance: 28 July 2023
Last Modified: 10 Oct 2023 19:11

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