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

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Abstract

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.

Graphical abstract: How the methyl group position influences the ultrafast deactivation in aromatic radicals

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Publication details

The article was received on 28 Sep 2018, accepted on 06 Dec 2018 and first published on 07 Dec 2018


Article type: Paper
DOI: 10.1039/C8CP06087H
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article
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    How the methyl group position influences the ultrafast deactivation in aromatic radicals

    M. Steglich, G. Knopp and P. Hemberger, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C8CP06087H

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