Photochemical deactivation pathways of the Ã-state allyl radical
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Jonas M. Hostettler, Luca Castiglioni, Andreas Bach, Peter Chen
Ab initio direct molecular dynamics with trajectory surface hopping methods simulates the photochemical deactivation pathways of the allyl radical, C3H5, following electronic excitation to the Ã-state. The electronically nonadiabatic dynamics mediated by two conical intersections produces predominantly hot ground state allyl radicals along both the disrotatory and conrotatory photochemical deactivation pathways with a near synchronous rotation of the terminal methylene groups. The electrocyclic transformation of the allyl radical to the cyclopropyl radical is a minor channel accounting for 8% of all trajectories with 98% of them following the disrotatory pathway.
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