Experimental and theoretical study of the electronic structure of HgO and Tl2O3
The electronic structures of HgO and Tl2O3 have been investigated by valence and core-level x-ray photoemission, x-ray absorption, and 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...
| Main Authors: | , , , , , , , |
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| Formato: | Journal article |
| Idioma: | English |
| Publicado: |
2005
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| _version_ | 1826261761211236352 |
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| author | Glans, P Learmonth, T Smith, K Guo, J Walsh, A Watson, G Terzi, F Egdell, R |
| author_facet | Glans, P Learmonth, T Smith, K Guo, J Walsh, A Watson, G Terzi, F Egdell, R |
| author_sort | Glans, P |
| collection | OXFORD |
| description | The electronic structures of HgO and Tl2O3 have been investigated by valence and core-level x-ray photoemission, x-ray absorption, and 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 partial density of states and therefore allows the extent of corresponding mixing of O 2p character into the 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 Tl2O3 are strongly perturbed by ionization of Tl core levels, giving rise to distinctive plasmon satellites in core x-ray photoemission spectroscopy. © 2005 The American Physical Society. |
| first_indexed | 2024-03-06T19:25:47Z |
| format | Journal article |
| id | oxford-uuid:1ba67127-f34f-4ac7-8f3a-b2507cf4ba05 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T19:25:47Z |
| publishDate | 2005 |
| record_format | dspace |
| spelling | oxford-uuid:1ba67127-f34f-4ac7-8f3a-b2507cf4ba052022-03-26T11:01:32ZExperimental and theoretical study of the electronic structure of HgO and Tl2O3Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:1ba67127-f34f-4ac7-8f3a-b2507cf4ba05EnglishSymplectic Elements at Oxford2005Glans, PLearmonth, TSmith, KGuo, JWalsh, AWatson, GTerzi, FEgdell, RThe electronic structures of HgO and Tl2O3 have been investigated by valence and core-level x-ray photoemission, x-ray absorption, and 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 partial density of states and therefore allows the extent of corresponding mixing of O 2p character into the 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 Tl2O3 are strongly perturbed by ionization of Tl core levels, giving rise to distinctive plasmon satellites in core x-ray photoemission spectroscopy. © 2005 The American Physical Society. |
| spellingShingle | Glans, P Learmonth, T Smith, K Guo, J Walsh, A Watson, G Terzi, F Egdell, R Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title | Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title_full | Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title_fullStr | Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title_full_unstemmed | Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title_short | Experimental and theoretical study of the electronic structure of HgO and Tl2O3 |
| title_sort | experimental and theoretical study of the electronic structure of hgo and tl2o3 |
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