Table 2. Relative Electronic Energiesa for the H2S + Cl Reactiong.
| reactants | RW | TS | PW | products | |
|---|---|---|---|---|---|
| H2S + Cl | H2S···Cl | HS···HCl | HS + HCl | ||
| CCSD(T)/VTZ | 0.00 | –28.29 | 7.74 | –56.10 | –44.90 |
| CCSD(T)/VQZ | 0.00 | –37.57 | 1.30 | –58.23 | –46.35 |
| CCSD(T)/V5Z | 0.00 | –41.32 | –0.84 | –59.11 | –46.95 |
| CCSD(T)/CBS | 0.00 | –44.84 | –3.10 | –60.10 | –47.51 |
| CBS+CV | 0.00 | –45.09 | –3.42 | –60.30 | –47.65 |
| CBS+CV+DBOC | 0.00 | –45.09 | –2.05 | –60.15 | –47.64 |
| CBS+CV+DBOC+rel | 0.00 | –45.11 | –2.31 | –59.98 | –47.45 |
| CBS+CV+DBOC+rel+fT+pQ | 0.00 | –45.14 | –3.41 | –60.09 | –47.45 |
| CBS+CV+DBOC+rel+fT+fQ | 0.00 | –45.11 | –3.33 | –60.08 | –47.44 |
| ChSb | 0.00 | –42.81 | –2.49 | –60.29 | –47.94 |
| [−42.94] | [−2.54] | [−60.41] | [−47.44] | ||
| jun-ChSb | 0.00 | –43.89 | –3.46 | –60.19 | –47.58 |
| (−43.81) | (−3.45) | (−60.18) | (−47.59) | ||
| [−43.89] | [−3.46] | [−60.19] | [−47.58] | ||
| ChS-F12a/F12b CBS(D,T)c | 0.00 | –44.64/–44.58 | –1.97/–1.93 | –59.80/–59.80 | –47.11/–47.15 |
| [−43.97/–43.91] | [−2.74/–2.70] | [−60.10/–60.10] | [−47.06/–47.09] | ||
| ChS-F12a/F12b CBS(T,Q)c | 0.00 | –43.87/–43.81 | –3.32/–3.29 | –60.33/–60.33 | –47.42/–47.46 |
| [−43.54/–43.48] | [−3.39/–3.35] | [−60.27/–60.27] | [−47.28/–47.31] | ||
| CBS-QB3d | 0.00 | –48.16 | –8.12 | –61.13 | –53.43 |
| revDSD-PBEP86-D3(BJ)e | 0.00 | –47.82 | –3.85 | –63.09 | –46.11 |
| (−45.50) | (−1.80) | (−59.43) | (−46.00) | ||
| QCISD/cc-pV(T+d)Zf | 0.00 | –23.14 | 20.17 | –43.76 | |
| PMP2/CBSf | 0.00 | –46.69 | –9.08 | –52.72 | |
| ae-CCSD(T)/CBSf | 0.00 | –46.48 | –7.57 | –48.16 |
Unless otherwise stated, reference geometries at the revDSD-PBEP86-D3(BJ)/jun-cc-pV(T+d)Z level.
Reference geometries at the same level as the energy evaluation. Extrapolation to the CBS limit in one step. Values within parentheses: revDSD-PBEP86-D3(BJ)/jun-cc-pV(T+d)Z geometries as reference. Values within square brackets: extrapolation to the CBS limit in two steps.
Reference geometries at the fc-CCSD(T)-F12/cc-pVDZ-F12 level. Extrapolation to the CBS limit in one step. Values within square brackets: Extrapolation to the CBS limit in two steps
Reference geometries at the B3LYP/6-31G(d) level.
Values obtained in conjunction with the jun-cc-pV(Q+d)Z basis set. Within parentheses: results for the jun-cc-pV(T+d)Z basis set. In both cases: reference structures at the revDSD-PBEP86-D3(BJ)/jun-cc-pV(T+d)Z level.
Results from ref (8).
Values in kJ mol–1.