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, Dynamique et Lasers (ex SPAM)
2 DyR - Dynamique Réactionnelle
IRAMIS - Institut Rayonnement Matière de Saclay, LIDyl - Laboratoire Interactions, Dynamique et Lasers (ex SPAM)
3 Institute of Physical and Theoretical Chemistry
4 SLIC - Serveurs Laser
IRAMIS - Institut Rayonnement Matière de Saclay, LIDyl - Laboratoire Interactions, Dynamique 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.
Document type :
Journal articles
Complete list of metadatas
https://hal-cea.archives-ouvertes.fr/cea-01536711
Contributor : Caroline Lebe <>
Submitted on : Monday, June 12, 2017 - 10:53:25 AM
Last modification on : Thursday, February 7, 2019 - 2:52:42 PM

Identifiers

Collections

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

Citation

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⟩

Export

BibTeX TEI DC DCterms EndNote

Share

Metrics

Record views

139

Contact

support.ccsd.cnrs.fr
hal.support@ccsd.cnrs.fr
Logo CCSD