A pulsed field ionization photoelectron-photoion coincidence study of the dissociative photoionization process D₂O + hvτ OD⁺ + D + e^-

We have examined the titled reaction near its threshold using the pulsed field ionization photoelectron-photoion coincidence method. The measured 0 K threshold (18.220±0.002 eV) has made possible the determination of more precise values for the 0 K bond dissociation energies for D-OD⁺ (5.584 ± 0.002 eV) and D-OD (5.191 ± 0.002 eV) and the 0 K heats of formation (ΔH^0, _f0 ^s) for OD ⁺ (308.83 ± 0.05 kcal/mol) and OD (8.38 ± 0.05 kcal/mol). We found that the available energetic data for the OD/OD⁺ and D₂O/D₂O⁺ system are in excellent agreement with those for the OH/OH⁺ and H₂O/H₂O⁺ system after taking into account the zero-point vibration energies of these species. © 2002 Published by Elsevier Science B.V.