Table II.
B3LYP reaction free energies in kcal/mol, using two different continuum models, SMD and PCM. ΔGg is obtained ΔGaqX is calculated as ΔGg + ΔΔGsolvX (X = PCM, SMD). The models included explicit first and second shell water molecules, except for the cases specified with a *, which contains only a first coordination sphere. For details see ref [10] and [11].
| SMD | PCM | ||
|---|---|---|---|
| Al-superoxide Formation Reactions | |||
| Al(H2O)6 3++O·2- | Al(O·2)(H2O)5 2+ + H2O | -8.3 | -15.2 |
| Al(OH)(H2O)5 2+ + O·2- | Al(O·2)(OH)(H2O)4 + + H2O | -8.7 | -13.5 |
| Al(O·2)(H2O)5 2+ + OH- | 13.5* | 11.6* | |
| Al(OH)2(H2O)4 + + O·2- | Al(O·2)(OH)2(H2O)3+H2O | -1.7 | -2.8 |
| Al(·O2)(OH)(H2O)4 + + OH- | 11.8* | 7.8* | |
| Al(OH)3(H2O)2+O·2 - | Al(O·2)(OH)3(H2O)- + H2O | -2 | -1.8 |
| Al(O·2)(OH)2(H2O)2 + OH- | 12.3* | 6.8* | |
| Al(OH)4 - + O·2- | Al(O·2)(OH)3- + OH- | 15.8 | 11.2 |
|
| |||
| Al-superoxide and Fe Redox Reactions | |||
| Fe3+ + AlO2·2+ | Fe2+ + Al3+ + O2 | -19.8 | -7.4 |
| Fe3+ + Al(OH)O2·+ | Fe2+ + Al(OH)2++O2 | -19.2 | -9.2 |
| Fe3+ + Al(OH)2O2· | Fe2+ + Al(OH)2 + + O2 | -18.9 | -12.1 |