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 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...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
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American Physical Society
2005
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| _version_ | 1797072766376083456 |
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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 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. |
| first_indexed | 2024-03-06T23:12:26Z |
| format | Journal article |
| id | oxford-uuid:65f1f631-4c91-4744-a646-9147bf963164 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:12:26Z |
| publishDate | 2005 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | oxford-uuid:65f1f631-4c91-4744-a646-9147bf9631642022-03-26T18:28:48ZExperimental and theoretical study of the electronic structure of HgO and Tl2O3Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:65f1f631-4c91-4744-a646-9147bf963164Inorganic chemistryChemistry & allied sciencesPhysicsEnglishOxford University Research Archive - ValetAmerican Physical Society2005Glans, PLearmonth, TSmith, KGuo, JWalsh, AWatson, GTerzi, FEgdell, RThe 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. |
| spellingShingle | Inorganic chemistry Chemistry & allied sciences Physics 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 |
| topic | Inorganic chemistry Chemistry & allied sciences Physics |
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