title: Atomic alignment effect in the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with oriented Ar (3P2, M(J) = 2).
abstract: The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)(5), Ni(CO)(4)) with the oriented Ar ((3)P(2), M(J) = 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar ((3)P(2), M(J) = 2) (rank 2 moment, a(2)) is found to be opposite for the two reaction systems; the Fe(CO)(5) reaction is favorable at the Π configuration (positive a(2)), while the Ni(CO)(4) reaction is favorable at the Σ configuration (negative a(2)). Moreover, a significant spin alignment effect (rank 4 moment, a(4)) is recognized only in the Ni(CO)(4) reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)(5) reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar ((3)P(2)) in the collision frame (L dependence), whereas the Ni(CO)(4) reaction is controlled by the configuration of the total angular moment J (including spin) of Ar ((3)P(2)) in the collision frame (J dependence). As the origin of J dependence observed only in the Ni(CO)(4) reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.
authors: Department of Chemistry, Graduate School of Science, Osaka University Toyonaka, Osaka 560-0043, Japan. ohyama@chem.sci.osaka-u.ac.jp
authors: H
authors: H
authors: Ohoyama
authors: Y
authors: Y
authors: Matsuura
mesh_terms: D001128:Argon / Q000737:chemistry*; D004735:Energy Transfer; D054354:Iron Carbonyl Compounds / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry*
chemical_list: D054354:Iron Carbonyl Compounds; D001128:Argon; D009532:Nickel