Table 2.
Quantum gas phase energetics and geometries. Gas phase stationary point calculations were performed at the 6-311+g(3df,2p) level of theory with a variety of quantum methods describing the attack of chloride anion on methyl chloride. Adiabatic energy results are presented as differences from experiment. Included with the methods tested in this study is the W1′ functional as a high-level benchmark for readers. All energies and energy differences are reported in kcal/mol. Bond distances are also given for the TS and IDC. All distances are reported in Å.
| Transition state |
Ion dipole comp. |
||||
|---|---|---|---|---|---|
| Method | dH | Barrier | dN | dL | Energy |
| Expt. | … | 13.6661, 62 | … | … | −10.5367 |
| W1′ | 2.3551 | (0.01) | 1.8461 | 3.1911 | (−0.05) |
| HF | 2.381 | (2.60) | 1.818 | 3.350 | (1.49) |
| MP2 | 2.287 | (2.22) | 1.806 | 3.151 | (−0.30) |
| B3LYP | 2.354 | (−4.57) | 1.844 | 3.180 | (0.71) |
| BH&HLYP | 2.562 | (−0.71) | 1.816 | 3.194 | (0.59) |
| ωB97x-D | 2.324 | (−0.58) | 1.817 | 3.186 | (0.04) |
| M06-2X | 2.300 | (0.06) | 1.817 | 3.101 | (−1.16) |
| AM1 | 2.154 | (−4.61) | 1.785 | 2.872 | (1.97) |
| MNDO | 2.148 | (−3.15) | 1.830 | 3.346 | (3.25) |
| MNDO/d | 2.173 | (5.93) | 1.805 | 3.516 | (4.45) |
| PM3 | 2.189 | (−4.00) | 1.806 | 2.843 | (1.65) |
| MeCl SRP | 2.300 | (0.04) | 1.819 | 3.088 | (−1.12) |
1
Geometries calculated at the B3LYP/cc-pVTZ+(X) level of theory.