Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 1, Issue 7, Pages 1036-1040Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz100196q
Keywords
-
Categories
Funding
- Alexander von Humboldt Foundation
- Deutsche Forschungsgemeinschaft [SFB 450, GO 1059/6-1]
- Freie Universitat Berlin
- Friedrich-Schiller-Universitat Jena
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available