Table 2. Interaction Energies Calculated (in kcal/mol) at MP2/aug-cc-pVTZ, MP2/CBS, and CCSD(T)/CBS Levels of Theory of the (PCl3)2 Optimized Homodimers under the Field-Free Condition and the Influence of the Negatively and Positively Directed EEF with Values Ranging from 0.002 to 0.008 au.
|
EMP2/aug-cc-pVTZ (kcal/mol) |
|||||||
|---|---|---|---|---|---|---|---|
| configuration | EEF (au) | distancea (Å) | BSSE-uncorrected | BSSE-corrected | estimated BSSE | EMP2/CBS (kcal/mol) | ECCSD(T)/CBS (kcal/mol) |
| σ-hole···σ-hole | –0.008 | 3.08 | –6.25 | –4.47 | 0.0028 | –5.47 | –3.50 |
| –0.004 | 3.15 | –5.41 | –3.72 | 0.0027 | –4.58 | –2.84 | |
| –0.002 | 3.17 | –5.21 | –3.55 | 0.0026 | –4.38 | –2.71 | |
| 0.000 | 3.16 | –5.16 | –3.49 | 0.0026 | –4.34 | –2.66 | |
| +0.002 | 3.16 | –5.22 | –3.55 | 0.0027 | –4.40 | –2.71 | |
| +0.004 | 3.15 | –5.39 | –3.71 | 0.0027 | –4.57 | –2.84 | |
| +0.008 | 3.08 | –6.25 | –4.50 | 0.0028 | –5.50 | –3.52 | |
| σ-hole···lp-hole | –0.008 | 4.59 | –3.97 | –2.97 | 0.0016 | –3.54 | –2.51 |
| –0.004 | 4.41 | –4.18 | –3.08 | 0.0017 | –3.69 | –2.60 | |
| –0.002 | 4.13 | –4.58 | –3.32 | 0.0020 | –3.98 | –2.78 | |
| 0.000 | 4.10 | –4.79 | –3.49 | 0.0021 | –4.16 | –2.92 | |
| +0.002 | 4.08 | –5.06 | –3.72 | 0.0021 | –4.43 | –3.15 | |
| +0.004 | 4.03 | –5.40 | –4.00 | 0.0022 | –4.78 | –3.41 | |
| +0.008 | 4.00 | –6.36 | –4.89 | 0.0023 | –5.74 | –4.26 | |
| lp-hole···lp-hole | –0.008 | 5.23 | –4.13 | –3.22 | 0.0015 | –3.86 | –2.78 |
| –0.004 | 5.23 | –3.93 | –3.04 | 0.0014 | –3.66 | –2.58 | |
| –0.002 | 5.23 | –3.88 | –2.99 | 0.0014 | –3.61 | –2.54 | |
| 0.000 | 5.23 | –3.87 | –2.98 | 0.0014 | –3.59 | –2.52 | |
| +0.002 | 5.23 | –3.88 | –2.98 | 0.0014 | –3.60 | –2.52 | |
| +0.004 | 5.23 | –3.93 | –3.04 | 0.0014 | –3.65 | –2.57 | |
| +0.008 | 5.23 | –4.13 | –3.22 | 0.0014 | –3.86 | –2.78 | |
a
Distances between the two interacted phosphorous atoms of the pnicogen homodimers within the modeled σ-hole···σ-hole, σ-hole···lp-hole, and lp-hole···lp-hole configurations.