Lawrence Berkeley National Laboratory

In a recent Letter,1 a set of minor inconsistencies have been found in the main body text and in the Supporting Information files; these are now thoroughly corrected. Thus, we highlight the sections where these changes apply. ¦ MAIN MANUSCRIPT BODY TEXT Abstract: The DO-D bond dissociation energy has been reported to be 5.41 ± 0.10 eV, while considering EA(O) in the original manuscript. However, EA(OD) should be used instead, thus leading to a bond dissociation energy of 5.28 ± 0.20 eV. Page 5365, left column, second paragraph; “From the appearance...” is reorganized and reads as follows: Taking the values in Table S4 together with the BDE, the enthalpy of reaction can be obtained from ?Hr(OH-) = D(H-OH) - EA(OH) = 3.34 eV. In the charge transfer process, if we add the potassium ionization energy, OH- is expected at 7.68 eV. The reactions threshold was obtained assuming no excess energy (E#), yet momentum conservation of the dissociating partners may impact on the lighter fragment kinetic energy, thus shifting the energy to a higher value. We note a difference of ~1.1 eV for the energy loss data, which is certainly plausible given the kinetic-energy release distribution of H- in Figure S3. Thus, from the appearance energy (AE) in the H2O energy loss spectrum (Figure 2) at ?E ˜ 8.8 eV, one can obtain the HO-H bond dissociation energy (BDE) by taking the potassium ionization energy and the data from Table S4,2 i.e., D(HO-H) = AE(OH-) - IE(K) + EA(OH) - E#, yielding therefore D(HO-H) = 5.19 ± 0.20 eV which is in good agreement with the values 5.15 eV (118.81 ± 0.07 kcal/ mol)3 and 5.17 eV.4 Following the same approach for D2O, the energy loss spectrum shows a threshold feature at ?E ˜ 9.0 eV. We obtain for the first time the DO-D bond dissociation energy to be D(DO-D) = 5.28 ± 0.20 eV. In D2O the DO-D energy value is slightly higher than the O-D bond dissociation energy (5.176 eV5), which is in agreement with its analogue H2O. Page 5366, right column, last paragraph; “Electronic state spectroscopy...” reads as follows: The electronic state spectroscopy of H2O/D2O was thoroughly discussed from the experimental K+ energy loss spectra obtained, from which the DO-D bond dissociation energy has been obtained for the first time to be 5.28 ± 0.20 eV. ¦ SUPPORTING INFORMATION Enthalpies of formation (?fHg°) in reactions 2a.1-2b.2 and 4a.1-4b.2 are actually enthalpies of reaction (?Hr). Table S2 decimal places for O- and OH- from H2O have been corrected; they now read 12.08 ± 0.20 and 7.80 ± 0.20.