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Four Plus Four State Degeneracies in the O−O Photolysis of Aromatic Endoperoxides

Mollenhauer, Doreen and Corral, Inés and González, Leticia – 2010

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.

Title
Four Plus Four State Degeneracies in the O−O Photolysis of Aromatic Endoperoxides
Author
Mollenhauer, Doreen and Corral, Inés and González, Leticia
Date
2010
Identifier
DOI: 10.1021/jz100196q
Source(s)
Citation
J. Phys. Chem. Lett. 2010, 1, 7, 1036-1040