title: Ni+ reactions with aminoacrylonitrile, a species of potential astrochemical relevance.
abstract: The reaction of aminoacrylonitrile, a species of astrochemical interest, with Ni(+)((2)D(5/2)) was investigated by means of mass spectrometry techniques and density functional theory calculations. The dominant fragmentations in the MIKE spectrum correspond to the loss of [C2,N,H3], HCN, and NH3, the loss of H2 being very minor. The structure and bonding of the different aminoacrylonitrile-Ni(+) complexes were investigated at the B3LYP/6-311G(d,p) level of theory. The same approach was employed in our survey of the corresponding potential energy surface. This survey indicates that the [C2,N,H3] neutral product can be formed either as ketenimine (CH2CNH) or acetonitrile. The formation of the latter is significantly more exothermic but involves slightly higher activation barriers; so very likely, both isomers are produced along the reaction process. The lost of HNC is not competitive with the loss of HCN, because when the former is formed the products lie higher in energy and the corresponding mechanisms involve energy barriers above the entrance channel. The loss of NH3 is associated with the formation of a complex between cyanoacetylene, HCCCN, which is very abundant in the interstellar media, and Ni(+).
authors.affiliation: Departamento de Quimica C-9, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid, Spain.
authors.forename: Al Mokhtar
authors.initials: AM
authors.lastname: Lamsabhi
authors.forename: Otilia
authors.initials: O
authors.lastname: Mó
authors.forename: Manuel
authors.initials: M
authors.lastname: Yáñez
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Salpin
authors.forename: Violette
authors.initials: V
authors.lastname: Haldys
authors.forename: Jeanine
authors.initials: J
authors.lastname: Tortajada
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Guillemin
mesh_terms: D003198:Computer Simulation; D003485:Cyanates / Q000737:chemistry; D005118:Extraterrestrial Environment / Q000737:chemistry*; D006856:Hydrogen Cyanide / Q000737:chemistry; D008024:Ligands; D013058:Mass Spectrometry; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D003485:Cyanates; D008024:Ligands; D009570:Nitriles; D009942:Organometallic Compounds; D006856:Hydrogen Cyanide; D009532:Nickel; C005057:isocyanic acid