Energy partitioning to product translation in the infrared multiphoton dissociation of diethyl ether

The infrared multiphoton decomposition of diethyl ether (DEE) has been investigated by the crossed laser-molecular beam technique. The center-of-mass product translational energy distributions (P (E primed) ) were measured for the two dissociation channels: (1) DEE > C2H5O + C2H5 and (2) DEE > C2H5OH + C2H4. The shape of the P(E') measured for the radical channel (1) is in agreement with prediction of statistical unimolecular rate theory. The translational energy released in the concerted reaction (2) peaks at 24 kcal/mole; this exceedingly high translational energy release with a relatively narrow distribution results from the recoil of the products from each other down the exit barrier. Applying statistical unimolecular rate theory, the average energy levels from which DEE dissociated to products are estimated using the measured P(E') for the radical channel (1).