Journal article

Authors list: Mollenhauer, D; Corral, I; Gonzalez, L

Publication year: 2010

Pages: 1036-1040

Journal: Journal of Physical Chemistry Letters

Volume number: 1

Issue number: 7

DOI Link: https://doi.org/10.1021/jz100196q

Publisher: American Chemical Society

Abstract: 

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.

Harvard Citation style: Mollenhauer, D., Corral, I. and Gonzalez, L. (2010) Four Plus Four State Degeneracies in the O−O Photolysis of Aromatic Endoperoxides, Journal of Physical Chemistry Letters, 1(7), pp. 1036-1040. https://doi.org/10.1021/jz100196q

APA Citation style: Mollenhauer, D., Corral, I., & Gonzalez, L. (2010). Four Plus Four State Degeneracies in the O−O Photolysis of Aromatic Endoperoxides. Journal of Physical Chemistry Letters. 1(7), 1036-1040. https://doi.org/10.1021/jz100196q