The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O
The vibrationally resolved Ã2Σ+ ← X2Σ+ transitions of Au+2N2 and Au+2N2O are reported together with a detailed characterization of important geometric and electronic properties, enabling a deep understanding of the bonding mechanism at the molecular level. Comparison with time-dependent density func...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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Scientific Research Publishing
2022
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| _version_ | 1826309304684118016 |
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| author | Förstel, M Nahvi, N-N Pollow, K Green, A Mackenzie, SR |
| author_facet | Förstel, M Nahvi, N-N Pollow, K Green, A Mackenzie, SR |
| author_sort | Förstel, M |
| collection | OXFORD |
| description | The vibrationally resolved Ã2Σ+ ← X2Σ+ transitions of Au+2N2 and Au+2N2O are reported together with a detailed characterization of important geometric and electronic properties, enabling a deep understanding of the bonding mechanism at the molecular level. Comparison with time-dependent density functional theory calculations reveals that the ligand stabilizes the Au+2 entity in the X2Σ+ state by donating electron density into the half-filled bonding orbital leading to the strengthening of the Au-Au, N-N and N-O bonds. This effect is reversed in the Ã2Σ+ state, where the Au-Au bonding orbital is already filled and the ligand destabilizes the Au-Au bond by donating into the antibonding orbitals of Au+2. The spectral detail obtained provides a deep understanding of the interplay of multiple electronic states in gas-phase metal-complex cations, opening the door for a systematic approach in the study of excited state reactivity in organometallic chemistry. |
| first_indexed | 2024-03-07T07:33:41Z |
| format | Journal article |
| id | oxford-uuid:a0687e7e-0264-48e4-9c4d-07c1c17ebaff |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:33:41Z |
| publishDate | 2022 |
| publisher | Scientific Research Publishing |
| record_format | dspace |
| spelling | oxford-uuid:a0687e7e-0264-48e4-9c4d-07c1c17ebaff2023-02-10T11:42:54ZThe impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2OJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a0687e7e-0264-48e4-9c4d-07c1c17ebaffEnglishSymplectic ElementsScientific Research Publishing2022Förstel, MNahvi, N-NPollow, KGreen, AMackenzie, SRThe vibrationally resolved Ã2Σ+ ← X2Σ+ transitions of Au+2N2 and Au+2N2O are reported together with a detailed characterization of important geometric and electronic properties, enabling a deep understanding of the bonding mechanism at the molecular level. Comparison with time-dependent density functional theory calculations reveals that the ligand stabilizes the Au+2 entity in the X2Σ+ state by donating electron density into the half-filled bonding orbital leading to the strengthening of the Au-Au, N-N and N-O bonds. This effect is reversed in the Ã2Σ+ state, where the Au-Au bonding orbital is already filled and the ligand destabilizes the Au-Au bond by donating into the antibonding orbitals of Au+2. The spectral detail obtained provides a deep understanding of the interplay of multiple electronic states in gas-phase metal-complex cations, opening the door for a systematic approach in the study of excited state reactivity in organometallic chemistry. |
| spellingShingle | Förstel, M Nahvi, N-N Pollow, K Green, A Mackenzie, SR The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title | The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title_full | The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title_fullStr | The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title_full_unstemmed | The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title_short | The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2 and Au2+N2O |
| title_sort | impact of optical excitation on the binding in complexes of the cationic gold dimer au2 n2 and au2 n2o |
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