Photochemical Dynamics on σπ Excited States in Ethylene Cation C2H4+

Baptiste Joalland (1) , Toshifumi Mori (2) , Todd J. Martínez (2) , Arthur G. Suits (1)

1 Wayne State University [Detroit]
2 Department of Chemistry [Stanford]

The ethylene cation C2H4+ is, with the isoelectronic neutral vinyl C2H3, the simplest organic π radical system: one electron populates a unique unique π orbital in the ground state electronic configuration.This system thus offers an opportunity to study in detail the complex electronic and vibronic dynamics in a prototype π radical. We present a combined electronic structure/photochemical dynamics study that investigates the non-adiabatic effects in ethylene cation C2H4+ after photoexcitation to its three first excited states. Emphasis is given on the role of the torsional coordinate which is associated to strong vibronic couplings.This study raises questions concerning the dynamics of highly electronically frustrated radicals and the influence of low-lying conical intersections on vibrational energy redistribution.

Domaines: Physique [physics]; Chimie

Baptiste Joalland, Toshifumi Mori, Todd J. Martínez, Arthur G. Suits. Photochemical Dynamics on σπ Excited States in Ethylene Cation C2H4+. Dynamics of Molecular Collisions, Jul 2013, Granlibakken, CA, United States. ⟨hal-01246966⟩