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• W2023441779 abstract "Abstract The experimental evidence indicates that the self-sensitized addition of molecular oxygen to a dissolved aromatic hydrocarbon M involves a reaction sequence in which the products of processes (1) and (2) are the reactants in processes (2) and (3), rather than the direct addition of O 2 3 Σ to either the excited singlet M(S 1 ) or triplet M(T 1 ) states of the acceptor. An orbital correlation scheme presented for the concerted addition process (3) and based on anthracene as a model acceptor with a “planar peroxide” complex configuration of highest symmetry shows that the complex or oxciplex states 3 (S 1 3 Σ) and 1.3 (T 1 3 Σ) must correlate endothermically with electronically excited states of the peroxide MO 2 . Arguments are given in support of the exchange mechanism for process (2) in non-polar solvents in which, for a similar oxciplex configuration, the final state correlates with that component of the O 2 1 Δ state which does not lead to formation of the MO 2 ground state 1 A 1 . Direct formation of MO 2 1 A 1 in processes (1) or (2) therefore requires electronic relaxation of the initially formed oxciplex states 3 (S 1 3 Σ) and 1 (T 1 3 Σ) which is either spin or orbitally forbidden but is achieved by dissociation and recombination of the molecular components." @default.
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• W2023441779 date "1975-01-01" @default.
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• W2023441779 title "The photoperoxidation of unsaturated organic molecules. XII. Dissociative oxciplex relaxation" @default.
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• W2023441779 doi "https://doi.org/10.1016/0047-2670(75)85043-x" @default.
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