How the methyl group position influences the ultrafast deactivation in aromatic radicals

文献情報

出版日 2018-12-07

DOI 10.1039/C8CP06087H

インパクトファクター 3.676

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要旨

Excited xylyl (methyl–benzyl) radical isomers have been studied by femtosecond time-resolved photoelectron spectroscopy and mass spectrometry. Depending on the substitution we find different deactivation channels after excitation into the D3(2A′′) state (310 nm, 4 eV). While the ortho and para isomer exhibit deactivation rates similar to the benzyl radical, meta-xylyl sticks out and depletes twice as fast into the vibrationally hot ground state. We found that a ring deformation mode rather than the methyl pseudorotation enables access to a conical intersection, which is responsible for the faster deactivation. Transitions in the photoelectron spectrum can be assigned to several Rydberg series with mostly d angular momentum components. Absorption of two 4 eV photons triggers hydrogen loss reactions on a femtosecond timescale.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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