A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+).
The electronic states of CeCp(3)(+) have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2009
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| _version_ | 1797105160374190080 |
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| author | Coates, R Coreno, M DeSimone, M Green, J Kaltsoyannis, N Kerridge, A Narband, N Sella, A |
| author_facet | Coates, R Coreno, M DeSimone, M Green, J Kaltsoyannis, N Kerridge, A Narband, N Sella, A |
| author_sort | Coates, R |
| collection | OXFORD |
| description | The electronic states of CeCp(3)(+) have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous conclusion that bands A and D in the valence photoelectron spectrum, despite their 3.2 eV separation, are produced by ionization of the single 4f electron of CeCp(3) [M. Coreno, M. de Simone, J. C. Green, N. Kaltsoyannis, N. Narband and A. Sella, Chem. Phys. Lett., 432, 2006, 17]. The origin of this effect is probed using the CASSCF/CASPT2 approach. While configurations based on the canonical CASSCF orbitals are found to be an unreliable description of the ground and excited states of CeCp(3)(+), the state-specific natural orbitals and their occupations yield greater insight, allowing us to characterize ion states in terms of the presence or otherwise of a Ce 4f-localised electron. Neither the CeCp(3)(+) ground state (assigned to band A), and two excited states ((1)A' and (1)A'', associated with band D), possess such a metal-based electron, as expected of f ionization. The (1)A' and (1)A'' states differ from the ground state in having a significant Ce 5d population, arising from Cp --> Ce charge transfer, which accompanies f ionization, and which is responsible for the energetic separation of bands A and D in the valence photoelectron spectrum. |
| first_indexed | 2024-03-07T06:43:29Z |
| format | Journal article |
| id | oxford-uuid:fa173edc-b2c6-41c2-86ca-6e15a1892083 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:43:29Z |
| publishDate | 2009 |
| record_format | dspace |
| spelling | oxford-uuid:fa173edc-b2c6-41c2-86ca-6e15a18920832022-03-27T13:03:02ZA mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+).Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:fa173edc-b2c6-41c2-86ca-6e15a1892083EnglishSymplectic Elements at Oxford2009Coates, RCoreno, MDeSimone, MGreen, JKaltsoyannis, NKerridge, ANarband, NSella, AThe electronic states of CeCp(3)(+) have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous conclusion that bands A and D in the valence photoelectron spectrum, despite their 3.2 eV separation, are produced by ionization of the single 4f electron of CeCp(3) [M. Coreno, M. de Simone, J. C. Green, N. Kaltsoyannis, N. Narband and A. Sella, Chem. Phys. Lett., 432, 2006, 17]. The origin of this effect is probed using the CASSCF/CASPT2 approach. While configurations based on the canonical CASSCF orbitals are found to be an unreliable description of the ground and excited states of CeCp(3)(+), the state-specific natural orbitals and their occupations yield greater insight, allowing us to characterize ion states in terms of the presence or otherwise of a Ce 4f-localised electron. Neither the CeCp(3)(+) ground state (assigned to band A), and two excited states ((1)A' and (1)A'', associated with band D), possess such a metal-based electron, as expected of f ionization. The (1)A' and (1)A'' states differ from the ground state in having a significant Ce 5d population, arising from Cp --> Ce charge transfer, which accompanies f ionization, and which is responsible for the energetic separation of bands A and D in the valence photoelectron spectrum. |
| spellingShingle | Coates, R Coreno, M DeSimone, M Green, J Kaltsoyannis, N Kerridge, A Narband, N Sella, A A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title | A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title_full | A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title_fullStr | A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title_full_unstemmed | A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title_short | A mystery solved? Photoelectron spectroscopic and quantum chemical studies of the ion states of CeCp3(+). |
| title_sort | mystery solved photoelectron spectroscopic and quantum chemical studies of the ion states of cecp3 |
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