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Issue 2, 2019
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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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Supplementary files

Article information


Submitted
28 Sep 2018
Accepted
06 Dec 2018
First published
07 Dec 2018

Phys. Chem. Chem. Phys., 2019,21, 581-588
Article type
Paper

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

M. Steglich, G. Knopp and P. Hemberger, Phys. Chem. Chem. Phys., 2019, 21, 581
DOI: 10.1039/C8CP06087H

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