Journal article
How the methyl group position influences the ultrafast deactivation in aromatic radicals.
- Steglich M Paul Scherrer Institute, CH-5232 Villigen-PSI, Switzerland. patrick.hemberger@psi.ch.
- Knopp G
- Hemberger P
- 2018-12-13
Published in:
- Physical chemistry chemical physics : PCCP. - 2019
English
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.
- Language
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- English
- Open access status
- closed
- Identifiers
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- DOI 10.1039/c8cp06087h
- PMID 30540303
- Persistent URL
- https://folia.unifr.ch/global/documents/291548
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