Ultrafast Relaxation Dynamics of the Ethylene Cation C₂ H₄+

Ludwig, André; Liberatore, Elisa; Herrmann, Jens; Kasmi, Lamia; López-Tarifa, Pablo; Gallmann, Lukas; Rothlisberger, Ursula; Keller, Ursula; Lucchini, Matteo (2016). Ultrafast Relaxation Dynamics of the Ethylene Cation C₂ H₄+. The journal of physical chemistry letters, 7(10), pp. 1901-1906. American Chemical Society 10.1021/acs.jpclett.6b00646

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We present a combined experimental and computational study of the relaxation dynamics of the ethylene cation. In the experiment, we apply an extreme-ultraviolet-pump/infrared-probe scheme that permits us to resolve time scales on the order of 10 fs. The photoionization of ethylene followed by an infrared (IR) probe pulse leads to a rich structure in the fragment ion yields reflecting the fast response of the molecule and its nuclei. The temporal resolution of our setup enables us to pinpoint an upper bound of the previously defined ethylene–ethylidene isomerization time to 30 ± 3 fs. Time-dependent density functional based trajectory surface hopping simulations show that internal relaxation between the first excited states and the ground state occurs via three different conical intersections. This relaxation unfolds on femtosecond time scales and can be probed by ultrashort IR pulses. Through this probe mechanism, we demonstrate a route to optical control of the important dissociation pathways leading to separation of H or H₂.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Institute of Applied Physics
08 Faculty of Science > Institute of Applied Physics > Lasers

UniBE Contributor:

Gallmann, Lukas


600 Technology > 620 Engineering
500 Science
500 Science > 530 Physics




American Chemical Society




Simone Corry

Date Deposited:

13 Jul 2017 09:35

Last Modified:

05 Dec 2022 15:03

Publisher DOI:






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