Table 1. Energies (kcal/mol) at Different Levels of Theory and Their Auxiliary Corrections (kcal/mol) for the Stationary Points and Product Channels of the Cl(2P3/2) + CH3CN Reaction Relative to the Reactants.
| MP2 | CCSD(T)-F12b |
|||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| stationary points | aVDZa | aVDZb | aVTZc | aVQZd | δ[T]e | δ[(Q)]f | Δcoreg | Δrelh | ΔSOi | classicalj | ΔZPEk | adiabaticl |
| H Abs TS | 7.28 | 7.43 | 7.98 | 7.93 | –0.36 | –0.26 | –0.04 | +0.07 | +0.80 | 8.15 | –4.39 | 3.76 |
| CH3 Sub C-side TS | 33.90 | 29.78 | 31.09 | 31.08 | –0.64 | –0.36 | +0.28 | +0.18 | +0.83 | 31.36 | –2.38 | 28.98 |
| H Sub W TS | 51.62 | 49.71 | 50.31 | 50.27 | –0.23 | –0.43 | +0.21 | +0.05 | +0.81 | 50.69 | –4.07 | 46.62 |
| CN Sub W TS | 57.51 | 54.73 | 54.82 | 54.83 | –1.32 | –0.67 | +0.65 | +0.01 | +0.78 | 54.27 | –1.73 | 52.54 |
| CH3 Sub N-side TS | 64.25 | 60.28 | 60.90 | 61.02 | –0.13 | –0.09 | +0.77 | –0.11 | +0.68 | 62.15 | –1.58 | 60.57 |
| H Sub FS TS | 67.41 | 65.12 | 65.93 | 65.92 | –0.39 | –0.48 | +0.18 | +0.00 | +0.83 | 66.05 | –4.25 | 61.80 |
| CN Sub FS TS | 77.14 | 74.40 | 75.05 | 75.07 | –1.49 | –0.86 | +0.64 | –0.10 | +0.81 | 74.08 | –1.63 | 72.45 |
| H Abs MIN | –6.95 | –9.26 | –8.33 | –8.43 | –0.45 | –0.09 | –0.07 | +0.27 | +0.83 | –7.94 | –3.50 | –11.44 |
| CH3 Sub C-side MIN | 25.53 | 20.72 | 22.29 | 22.25 | +0.02 | –0.23 | +0.12 | +0.20 | +0.83 | 23.19 | –3.90 | 19.28 |
| H Sub W MIN | 26.00 | 27.29 | 28.83 | 28.80 | +0.15 | –0.23 | +0.04 | +0.18 | +0.83 | 29.77 | –4.83 | 24.95 |
| CH3 Sub N-side MIN | 75.18 | 64.14 | 65.81 | 65.87 | –0.15 | –0.05 | +0.51 | +0.16 | +0.83 | 67.17 | –4.55 | 62.62 |
| H Sub FS MIN | 25.98 | 27.11 | 28.76 | 28.73 | +0.15 | –0.23 | +0.04 | +0.18 | +0.83 | 29.70 | –4.79 | 24.91 |
| CN Sub FS MIN | 38.82 | 34.44 | 35.21 | 35.22 | –1.17 | –0.45 | +0.52 | +0.11 | +0.83 | 35.06 | –0.71 | 34.35 |
| HCl + CH2CN | –0.78 | –3.82 | –3.11 | –3.21 | –0.48 | –0.06 | +0.00 | +0.23 | +0.83 | –2.68 | –4.74 | –7.42 |
| ClCN + CH3 | 27.06 | 22.05 | 23.55 | 23.48 | +0.02 | –0.22 | +0.13 | +0.20 | +0.83 | 24.43 | –4.30 | 20.13 |
| ClCH2CN + H | 26.30 | 27.65 | 29.19 | 29.14 | +0.15 | –0.22 | +0.04 | +0.18 | +0.83 | 30.12 | –5.18 | 24.94 |
| ClNC + CH3 | 76.55 | 65.41 | 66.89 | 66.91 | –0.16 | –0.03 | +0.52 | +0.17 | +0.83 | 68.25 | –4.94 | 63.31 |
| CH3Cl + CN | 44.32 | 38.94 | 39.51 | 39.44 | –1.59 | –0.48 | +0.60 | +0.15 | +0.83 | 38.96 | –1.60 | 37.36 |
MP2/aug-cc-pVDZ relative energies obtained at MP2/aug-cc-pVDZ geometries.
CCSD(T)-F12b/aug-cc-pVDZ relative energies obtained at CCSD(T)-F12b/aug-cc-pVDZ geometries.
CCSD(T)-F12b/aug-cc-pVTZ relative energies obtained at CCSD(T)-F12b/aug-cc-pVTZ geometries.
CCSD(T)-F12b/aug-cc-pVQZ relative energies obtained at CCSD(T)-F12b/aug-cc-pVTZ geometries.
CCSDT – CCSD(T) obtained at CCSD(T)-F12b/aug-cc-pVTZ geometries with the aug-cc-pVDZ basis set.
CCSDT(Q) – CCSDT obtained at CCSD(T)-F12b/aug-cc-pVTZ geometries with the aug-cc-pVDZ basis set.
Core correlation corrections obtained as the differences between all-electron and frozen-core CCSD(T)-F12b/cc-pCVTZ-F12 relative energies at CCSD(T)-F12b/aug-cc-pVTZ geometries.
Scalar relativistic effects obtained as the difference between DK-AE-CCSD(T)/aug-cc-pwCVTZ-DK and AE-CCSD(T)/aug-cc-pwCVTZ relative energies at CCSD(T)-F12b/aug-cc-pVTZ geometries.
Spin–orbit (SO) corrections obtained as the differences between the SO and non-SO ground-state MRCI+Q/aug-cc-pwCVTZ relative energies at CCSD(T)-F12b/aug-cc-pVTZ geometries.
Benchmark classical relative energies obtained as CCSD(T)-F12b/aug-cc-pVQZ relative energies + δ[T] (e) + δ[(Q)] (f) + Δcore (g) + Δrel (h) + ΔSO (i).
Zero-point energy (ZPE) corrections obtained at CCSD(T)-F12b/aug-cc-pVTZ.
Benchmark vibrationally adiabatic relative energies obtained as classical relative energies (j) + ΔZPE (k).