Photochemical deactivation pathways of the A-state allyl radical.
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.
Hostettler
Jonas M
JM
Laboratorium für Organische Chemie, ETH Zürich, 8093 Zürich, Switzerland.
Castiglioni
Luca
L
Bach
Andreas
A
Chen
Peter
P