Photochemical deactivation pathways of the Ã-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 predom...

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Bibliographic Details
Published inPhysical chemistry chemical physics : PCCP Vol. 11; no. 37; pp. 8262 - 8265
Main Authors HOSTETTLER, Jonas M, CASTIGLIONI, Luca, BACH, Andreas, CHEN, Peter
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 01.01.2009
Subjects
Chemistry
Exact sciences and technology
General and physical chemistry
Deactivation
Electronically excited state
Molecular dynamics
Theoretical study
Ground state
Ab initio calculations
Trajectory
Rotation
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Summary: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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ISSN:1463-9076
1463-9084
DOI:10.1039/b909830e