Experimental and theoretical study of the electronic structure of HgO and Tl2O3

Journal article

The electronic structures of HgO and Tl2O3 have been investigated by valence and core-level x-ray emission spectroscopies. Valence-band photoemission under Al Kα excitation is dominated by the metal 5d partial density of states and thus provides a sensitive probe of shallow core mixing into the O 2p valence-band states. Conversely O K shell emission is determined by the O 2p shallow core states to be measured. The experimental work is supported by band-structure calculations carried out within the framework of density-functional theory. It is shown that the bonding in HgO involves significant mixing between O 2p states and both Hg 6s and shallow core 5d states: the calculated O 2p partial density of states mirrors the O K shell emission spectrum and reveals significant O 2p character within the shallow core Hg 5d states. There is, however, little direct on-site mixing between the Hg 6s and 5d states. In Tl2O3, the hybridization of the deeper metal 5d states with O 2p states is much less pronounced than in HgO. Moreover, the states at the bottom of what is conventionally regarded as the O 2p valence band are found in fact to have very strong Tl 6s atomic character. The photoemission spectrum of Tl2O3 shows a well-defined metallic Fermi edge: the shape of the structure around the photoemission onset suggests that the metallic nature of Tl2O3 arises from an occupation of states above the main valence-band edge, probably arising from oxygen vacancy defects. The conduction electrons of Tl2)3 are strongly perturbed by ionization of Tl core levels, giving rise to distinctive plasmon satellites in core x-ray photoemission spectroscopy.

Authors: Glans, P; Learmonth, T; Smith, K; Guo, J; Walsh, A

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Physical Society
• Journal: Physical Review B
• Volume: 71
• Issue: 23
• Pages: 235109
• Publication date: 2005-06-01
• Edition: Publisher's version
• DOI: 10.1103/PhysRevB.71.235109
• EISSN: 1550-235x
• ISSN: 1098-0211
• Language: English
• Keywords: x-ray photoemission spectra; electronic structure; x-ray emission spectra; x-ray absorption
• Subjects: Inorganic chemistry; Physics; Chemistry & allied sciences