Photochemical Dynamics of Ethylene Cation C2H4

• Published in: The journal of physical chemistry letters Vol. 5; no. 8; pp. 1467 - 1471
• Main Authors: Joalland, Baptiste, Mori, Toshifumi, Martínez, Todd J, Suits, Arthur G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.04.2014
• Subjects: Chemical Sciences; Physics; Spectroscopy, Photochemistry, and Excited States; conical intersections; hindered rotation; excited states; Jahn−Teller effect; nonadiabatic transitions
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/jz500352x

We present a theoretical study of the nonadiabatic effects in ethylene cation C2H4 +, the simplest π radical cation, after photoexcitation to its three lowest doublet excited states. Two families of conical intersections are found, with minimum energy structures characterized by planar and twisted geometries. Ab initio multiple spawning dynamical calculations suggest that the competition between these relaxation pathways depends strongly on the initial excited state, with excited state lifetimes in the 30–60 fs range. Ultrafast decay via planar geometries deposits the molecule near a bridged minimum on the ground state, allowing prompt H migration events. The alternative pathway mediated by torsional motion induces important backspawned population transfer promoted by hindered rotations. The results allow us to revisit earlier vibrationally-mediated photodissociation experiments and shed light on the electronic relaxation dynamics of a prototypical radical cation subject to strong vibronic interactions.