期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 1, 期 7, 页码 1036-1040出版社
AMER CHEMICAL SOC
DOI: 10.1021/jz100196q
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资金
- Alexander von Humboldt Foundation
- Deutsche Forschungsgemeinschaft [SFB 450, GO 1059/6-1]
- Freie Universitat Berlin
- Friedrich-Schiller-Universitat Jena
The thermal and photochemical O-O bond dissociation mechanisms in the aromatic oxygen carrier photosensitizer anthracene-9,10-endoperoxide have been elucidated using high-level multiconfigurational ab initio calculations (CASSCF and MS-CASPT2). Our results show that in both the thermal and the photochemical pathways, the system proceeds through a degeneracy of four singlet plus four triplet states. This high-order degeneracy provides an efficient funnel for radiationless deactivation from the lowest excited state, indicating that the system does not dissociate in the excited-state manifold but that the products are rather formed in the electronic ground state. Accordingly, the homolysis of the peroxide group leads to four plus four ground-state biradicals, which are the precursors of the experimentally observed rearrangement products.
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