Table 1. Relative Electronic Energies (in kcal/mol) and Gibbs Free Energies (at 298 K and 1 atm Reference Pressure) for the Reaction Route 3(RO···OR′) ⇒ RO + R′O Computed at UωB97X-D/aug-cc-pVTZ (DFT) and ROHF-ROCCSD(T)-F12a/cc-pVDZ-F12 (F12) Levels of Theory.
| 3(RO···OR′) cluster | ΔEDFT (kcal/mol) | ΔGDFT (kcal/mol) | ΔEF12 (kcal/mol) | ΔGF12 (=ΔGDFT + ΔEF12 – ΔEDFT) (kcal/mol) | O···O distance in (Å) |
|---|---|---|---|---|---|
| MeO···OMea | +3.32 | –5.38 | +3.15 | –5.55 | 3.49 |
| MeO···OEt | +4.57 | –3.91 | +7.07 | –1.41 | 3.49 |
| MeO···OiPr | +3.70 | –4.49 | +3.16 | –5.03 | 3.47 |
| MeO···OAce | +3.34 | –5.08 | +3.63 | –4.78 | 6.14 |
| MeO···OBuOH | +6.99 | –4.13 | +6.05 | –5.07 | 3.35 |
| MeO···OiPrOH | +7.87 | –3.21 | +6.82 | –4.27 | 3.35 |
| EtO···OiPr | +5.22 | –4.17 | +7.61 | –1.79 | 3.59 |
| EtO···OAce | +5.98 | –2.83 | +9.42 | +0.60 | 4.21 |
| EtO···OBuOH | +8.62 | –2.48 | +10.55 | –0.54 | 3.27 |
| EtO···OiPrOH | +9.49 | –1.40 | +11.29 | +0.41 | 3.27 |
| iPrO···OAce | +5.83 | –4.11 | +5.85 | –4.09 | 4.16 |
| iPrO···OiPrOH | +8.98 | –2.12 | +7.25 | –3.85 | 3.31 |
| iPrO···OBuOH | +8.33 | –3.15 | +6.24 | –5.24 | 3.33 |
| AceO···iPrOH | +9.59 | –2.54 | +7.52 | –4.61 | 3.42 |
| AceO···OBuOH | +9.90 | –2.73 | +7.66 | –4.96 | 3.43 |
a
MeO···OMe data from our previous study,9 provided here for reference and comparison.