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Low energy crossed beam studies of OD+ and D2O+ with C2H4: covalent and electrostatic complexes

Density functional theory (DFT) calculations are used in conjunction with low-energy crossed beam studies of the ion-molecule reactions of D2O+ and OD+ with C2H4 to probe collision dynamics, particularly the role that electrostatic and covalent intermediates play. In the D+-transfer reaction initiated with D2O+, an electrostatic complex formed when the transferred species approaches the perpendicular bisector of the C=C bond plays an important role. Observation of C2H4D+ products with excitation in the ν10 stretching mode, in which the bridging D-atom moves along the perpendicular bisector, provides support for this complex. In the OD+ reaction, evidence for the occurrence of reaction on the ground singlet surface following internal conversion comes from the observation of a transient complex living ∼100 fs. The DFT calculations show that the rate-limiting step corresponds to ring-opening and H/D exchange initiated in an ethylene oxide species with D+ bound to the oxygen atom. Computed lifetimes are in agreement with experiment. This study provides an example of how high-resolution crossed beam studies in conjunction with quantum chemical calculations, can provide a detailed understanding of collision dynamics in systems of moderate complexity. New experimental developments, including the application of velocity space imaging methods, as well as the production of beams of free radicals, will lead to a greater understanding of energy and angular momentum disposal in systems of chemical relevance.