Bimolecular reactions of CH2CN2+ with Ar, N2 and CO: reactivity and dynamics

Abstract

The reactivity, energetics and dynamics of bimolecular reactions between CH₂CN²⁺ and three neutral species (Ar, N₂ and CO) have been studied using a position sensitive coincidence methodology at centre-of-mass collision energies of 4.3–5.0 eV. This is the first study of bimolecular reactions involving CH₂CN²⁺, a species relevant to the ionospheres of planets and satellites, including Titan. All of the collision systems investigated display two collision-induced dissociation (CID) channels, resulting in the formation of C⁺ + CH₂N⁺ and H⁺ + HC₂N⁺. Evidence for channels involving further dissociation of the CID product HC₂N⁺, forming H + CCN⁺, were detected in the N₂ and CO systems. Proton-transfer from the dication to the neutral species occurs in all three of the systems via a direct mechanism. Additionally, there are product channels resulting from single electron transfer following collisions of CH₂CN²⁺ with both N₂ and CO, but interestingly no electron transfer following collisions with Ar. Electronic structure calculations of the lowest energy electronic states of CH₂CN²⁺ reveal six local geometric minima: both doublet and quartet spin states for cyclic, linear (CH₂CN), and linear isocyanide (CH₂NC) molecular geometries. The lowest energy electronic state was determined to be the doublet state of the cyclic dication. The ready generation of C⁺ ions by collision-induced dissociation suggests that the cyclic or linear isocyanide dication geometries are present in the [CH₂CN]²⁺ beam.