TY - JOUR
T1 - Experimental investigation of the reaction of helium ions with dimethyl ether
T2 - stereodynamics of the dissociative charge exchange process
AU - Cernuto, Andrea
AU - Tosi, Paolo
AU - Martini, Luca Matteo
AU - Pirani, Fernando
AU - Ascenzi, Daniela
PY - 2017/8/2
Y1 - 2017/8/2
N2 - The fate of dimethyl ether (DME, CH3OCH3) in collisions with He+ ions is of high relevance for astrochemical models aimed at reproducing the abundances of complex organic molecules in the interstellar medium. Here we report an investigation on the reaction of He+ ions with DME carried out using a Guided Ion Beam Mass Spectrometer (GIB-MS), which allows the measurement of reactive cross-sections and branching ratios (BRs) as a function of the collision energy. We obtain insights into the dissociative charge (electron) exchange mechanism by investigating the nature of the non-adiabatic transitions between the relevant potential energy surfaces (PESs) in an improved Landau-Zener approach. We find that the large interaction anisotropy could induce a pronounced orientation of the polar DME molecule in the electric field generated by He+ so that at short distances the collision complex is confined within pendular states, a particular case of bending motion, which gives rise to intriguing stereodynamic effects. The positions of the intermolecular potential energy curve crossings indicate that He+ captures an electron from an inner valence orbital of DME, thus causing its dissociation. In addition to the crossing positions, the symmetry of the electron density distribution of the involved DME orbitals turns out to be a further major point affecting the probability of electron transfer. Thus, the anisotropy of the intermolecular interaction and the electron densities of the orbitals involved in the reaction are the key "ingredients" for describing the dynamics of this dissociative charge transfer.
AB - The fate of dimethyl ether (DME, CH3OCH3) in collisions with He+ ions is of high relevance for astrochemical models aimed at reproducing the abundances of complex organic molecules in the interstellar medium. Here we report an investigation on the reaction of He+ ions with DME carried out using a Guided Ion Beam Mass Spectrometer (GIB-MS), which allows the measurement of reactive cross-sections and branching ratios (BRs) as a function of the collision energy. We obtain insights into the dissociative charge (electron) exchange mechanism by investigating the nature of the non-adiabatic transitions between the relevant potential energy surfaces (PESs) in an improved Landau-Zener approach. We find that the large interaction anisotropy could induce a pronounced orientation of the polar DME molecule in the electric field generated by He+ so that at short distances the collision complex is confined within pendular states, a particular case of bending motion, which gives rise to intriguing stereodynamic effects. The positions of the intermolecular potential energy curve crossings indicate that He+ captures an electron from an inner valence orbital of DME, thus causing its dissociation. In addition to the crossing positions, the symmetry of the electron density distribution of the involved DME orbitals turns out to be a further major point affecting the probability of electron transfer. Thus, the anisotropy of the intermolecular interaction and the electron densities of the orbitals involved in the reaction are the key "ingredients" for describing the dynamics of this dissociative charge transfer.
UR - http://www.scopus.com/inward/record.url?scp=85027342114&partnerID=8YFLogxK
U2 - 10.1039/c7cp00827a
DO - 10.1039/c7cp00827a
M3 - Article
C2 - 28277582
AN - SCOPUS:85027342114
SN - 1463-9076
VL - 19
SP - 19554
EP - 19565
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 30
ER -