title: Selective control over fragmentation reactions in polyatomic molecules using impulsive laser alignment.
abstract: We investigate the possibility of using molecular alignment for controlling the relative probability of individual reaction pathways in polyatomic molecules initiated by electronic processes on the few-femtosecond time scale. Using acetylene as an example, it is shown that aligning the molecular axis with respect to the polarization direction of the ionizing laser pulse does not only allow us to enhance or suppress the overall fragmentation yield of a certain fragmentation channel but, more importantly, to determine the relative probability of individual reaction pathways starting from the same parent molecular ion. We show that the achieved control over dissociation or isomerization pathways along specific nuclear degrees of freedom is based on a controlled population of associated excited dissociative electronic states in the molecular ion due to relatively enhanced ionization contributions from inner valence orbitals.
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Xinhua
authors.initials: X
authors.lastname: Xie
authors.affiliation: Institute for Theoretical Physics, Vienna University of Technology, A-1040 Vienna, Austria and Institute for Physical Chemistry, Friedrich-Schiller University Jena, D-07743 Jena, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Doblhoff-Dier
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria and State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun 130012, China.
authors.forename: Huailiang
authors.initials: H
authors.lastname: Xu
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Stefan
authors.initials: S
authors.lastname: Roither
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Markus S
authors.initials: MS
authors.lastname: Schöffler
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Daniil
authors.initials: D
authors.lastname: Kartashov
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Sonia
authors.initials: S
authors.lastname: Erattupuzha
authors.affiliation: Institute of Optics and Quantum Electronics, Friedrich-Schiller-University Jena, D-07743 Jena, Germany.
authors.forename: Tim
authors.initials: T
authors.lastname: Rathje
authors.affiliation: Institute of Optics and Quantum Electronics, Friedrich-Schiller-University Jena, D-07743 Jena, Germany and Helmholtz Institute Jena, D-07743 Jena, Germany.
authors.forename: Gerhard G
authors.initials: GG
authors.lastname: Paulus
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Tokyo 113-0033, Japan.
authors.forename: Kaoru
authors.initials: K
authors.lastname: Yamanouchi
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Andrius
authors.initials: A
authors.lastname: Baltuška
authors.affiliation: Institute for Physical Chemistry, Friedrich-Schiller University Jena, D-07743 Jena, Germany and Abbe Center of Photonics, Friedrich-Schiller-University Jena, D-07743 Jena, Germany.
authors.forename: Stefanie
authors.initials: S
authors.lastname: Gräfe
authors.affiliation: Photonics Institute, Vienna University of Technology, A-1040 Vienna, Austria.
authors.forename: Markus
authors.initials: M
authors.lastname: Kitzler
mesh_terms: D000114:Acetylene / Q000737:chemistry*; D000465:Algorithms; D007834:Lasers; D055668:Photochemical Processes; D010777:Photochemistry / Q000379:methods*
chemical_list: D000114:Acetylene