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Updated: Jun 20, 2026

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
Published on: April 15, 2013
Photochemical deactivation pathways of the A-state allyl radical
Jonas M Hostettler1, Luca Castiglioni, Andreas Bach
1Laboratorium für Organische Chemie, ETH Zürich, 8093 Zürich, Switzerland.
Abstract:
Ab initio direct molecular dynamics with trajectory surface hopping methods simulates the photochemical deactivation pathways of the allyl radical, C(3)H(5), following electronic excitation to the A-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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