title: Photodissociation dynamics of propargylene, HCCCH.
abstract: We report a joint theoretical and experimental study on the photodissociation of the C3H2 isomer propargylene, HCCCH, combining velocity map imaging with nonadiabatic trajectory surface hopping calculations. Propargylene loses an H-atom, after laser excitation at around 250 nm, presumably to the T6 state. The photofragment angular distribution exhibits only a very small anisotropy, but the H-atom translational energy distribution extends to high energies and shows an expectation value of 〈fT〉, the fraction of excess energy released as translation, of 48%, outside the range expected for a statistical reaction mechanism. The computations suggest a predissociation in the T4-T6 state and lead to a translational energy distribution and photofragment angular distribution that match the experimentally observed ones very well.
authors.affiliation: Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany. roland.mitric@uni-wuerzburg.de ingo.fischer@uni-wuerzburg.de.
authors.forename: Jens
authors.initials: J
authors.lastname: Giegerich
authors.forename: Jens
authors.initials: J
authors.lastname: Petersen
authors.forename: Roland
authors.initials: R
authors.lastname: Mitrić
authors.forename: Ingo
authors.initials: I
authors.lastname: Fischer