Table 12. Deviations for 16 Reaction Energies of Neutral Closed Shell Phosphorus Containing Molecules Compared to G3B3a.
| reaction | G3B3 | B3LYPb | B3LYPc | PBEc | PM6d | PDDGd | MIO | 3OB | 3OB/OPhyd |
|---|---|---|---|---|---|---|---|---|---|
| PH3 + H2O → H2P–OH + H2 | 9.4 | –0.0 | –2.4 | –2.7 | –7.5 | –5.5 | –27.2 | –0.5 | –10.9 |
| PH3 + H2O → HP=O + 2H2 | 40.1 | +2.5 | –2.4 | –2.3 | –2.3 | –11.7 | –39.6 | –10.3 | –18.5 |
| PH3 + CH4 → H3C–PH2 + H2 | 13.7 | +2.5 | +2.2 | +0.5 | –11.6 | –13.4 | –8.7 | –4.4 | –4.4 |
| PH3 + C2H6 → H3C–PH2 + CH4 | –4.6 | +0.7 | +1.2 | +0.9 | –2.1 | –8.9 | –7.5 | –2.8 | –2.8 |
| (CH3)2P=O + 2H2O → HP(=O)(OH)2 + 2CH4 | –36.0 | –4.0 | –9.8 | –7.2 | +22.5 | +12.1 | –41.5 | +3.3 | –16.1 |
| PH3 + 4H2O → H3PO4 + 4H2 | –31.5 | +9.3 | –4.5 | –7.6 | +4.3 | –17.4 | –92.7 | –2.1 | –39.0 |
| H2P(=O)OH + H2O → HP(=O)(OH)2 + H2 | –16.0 | +1.9 | –1.6 | –2.2 | –1.9 | –0.7 | –24.2 | +2.7 | –6.8 |
| HP(=O)(OH)2 + H2O → H3PO4 + H2 | –12.1 | +2.3 | –1.1 | –1.5 | –3.2 | +0.7 | –32.3 | –5.8 | –15.1 |
| P(OH)3 + H2O → H3PO4 + H2 | –24.1 | +8.3 | +3.1 | +2.1 | +14.6 | +4.0 | –18.7 | –7.2 | –13.2 |
| (HO)2(O=)P–P(=O)(OH)2 + 2H2O → 2H3PO4 + H2 | –29.5 | –0.3 | –3.7 | +0.8 | –6.3 | +16.3 | –60.8 | –21.8 | –39.7 |
| 2PH3 → H2P–PH2 + H2 | 4.3 | +2.0 | +2.0 | –0.3 | –18.0 | –37.9 | –21.2 | –8.1 | –8.1 |
| PH3 + NH3 → NP + 3H2 | 59.8 | +8.7 | +2.9 | +4.0 | –4.2 | –35.8 | –12.3 | –6.4 | –6.4 |
| PH3 + NH3 → HN–PH + 2H2 | 48.3 | +4.0 | +1.7 | +1.1 | –8.4 | –20.1 | –2.5 | –1.5 | –1.5 |
| PH3 + NH3 → H2N–PH2 + H2 | 11.4 | +1.7 | +0.6 | –0.0 | –14.0 | –11.3 | +3.9 | +1.2 | +1.2 |
| P(NH2)3 + 3H2O → P(OH)3 + 3NH3 | –20.2 | –6.5 | –11.1 | –9.3 | +20.4 | +4.2 | –92.7 | –8.6 | –39.6 |
| H3PO4 + H2O → P(OH)5 | 0.4 | +0.7 | –4.8 | –8.8 | –18.4 | +16.1 | –3.6 | +19.3 | +4.8 |
| MAD | 3.5 | 3.4 | 3.2 | 10.0 | 13.5 | 30.6 | 6.6 | 14.3 | |
| MAX | 9.3 | 11.1 | 9.3 | 22.5 | 37.9 | 92.7 | 21.8 | 39.7 |
a
Energies are calculated at 0 K excluding zero point energy and thermal corrections. All numbers are given in kcal/mol.
b
Basis set is cc-pVTZ.
c
Basis set is 6-31G(d).
d
Heats of formation for H2 are calculated as −26 and −22 kcal/mol for PM6 and PDDG. To correct for this exceptional error, this value is set to 0.0 kcal/mol.