Femtosecond dynamics of the 2-methylallyl radical: A computational and experimental study

A. Röder 1, 2, 3 K. Issler 3 L. Poisson 2, 1 A. Humeniuk 3 M. Wohlgemuth 3 M. Comte 4, 1 F. Lepetit 1, 4 I. Fischer 3 R. Mitric 3 J. Petersen 3
1 LIDyl - Laboratoire Interactions, Dynamiques et Lasers (ex SPAM)
2 DyR - Dynamique Réactionnelle
IRAMIS - Institut Rayonnement Matière de Saclay, LIDyl - Laboratoire Interactions, Dynamiques et Lasers (ex SPAM)
3 Institute of Physical and Theoretical Chemistry
4 SLIC - Serveurs Laser
IRAMIS - Institut Rayonnement Matière de Saclay, LIDyl - Laboratoire Interactions, Dynamiques et Lasers (ex SPAM)
Abstract : We investigate the photodynamics of the 2-methylallyl radical by femtosecond time-resolved photoelectron imaging. The experiments are accompanied by field-induced surface hopping dynamics calculations and the simulation of time-resolved photoelectron intensities and anisotropies, giving insight into the photochemistry and nonradiative relaxation of the radical. 2-methylallyl is excited at 236 nm, 238 nm, and 240.6 nm into a 3p Rydberg state, and the subsequent dynamics is probed by multiphoton ionization using photons of 800 nm. The photoelectron image exhibits a prominent band with considerable anisotropy, which is compatible with the result of theory. The simulations show that the initially excited 3p state is rapidly depopulated to a 3s Rydberg state, from which photoelectrons of high anisotropy are produced. The 3s state then decays within several 100 fs to the D1 (nπ π) state, followed by the deactivation of the D1 to the electronic ground state on the ps time scale.
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Journal articles
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https://hal-cea.archives-ouvertes.fr/cea-01536711
Contributor : Caroline Lebe <>
Submitted on : Monday, June 12, 2017 - 10:53:25 AM
Last modification on : Monday, September 2, 2019 - 5:32:02 PM

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CEA | CNRS | DSM-IRAMIS | IRAMIS-LIDYL | UNIV-PARIS-SACLAY | CEA-DRF | CEA-UPSAY

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A. Röder, K. Issler, L. Poisson, A. Humeniuk, M. Wohlgemuth, et al.. Femtosecond dynamics of the 2-methylallyl radical: A computational and experimental study . Journal of Chemical Physics, American Institute of Physics, 2017, 147, pp.013902. ⟨10.1063/1.4974150⟩. ⟨cea-01536711⟩

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