Energy decomposition analysis (BP86-D3(BJ)/QZ4P) of the ground state (GS) and the inversion transition state (TS) of SiH4 and SiF4. Individual angular and radial contributions were derived with the help of a D4h symmetric structure with the bond lengths of the ground state (TS′). All numbers are given in kJ mol−1. The values in parenthesis specify the contribution of the interaction and the preparation energy to the inversion barrier (Δ(ΔEInt + ΔEPrep), see Chapter S15 in the ESI for details). The values in brackets state the relative electrostatic and orbital contribution to the difference in interaction energy.
| |||||||
|---|---|---|---|---|---|---|---|
| GS | TS′ | TS | Angular contribution (GS → TS′, ΔΔEA) | Radial contribution (TS' → TS, ΔΔER) | Total (GS → TS, ΔΔE) | ||
| SiH4 | ΔEPauli | 692.0 | 709.5 | 582.4 | 17.5 | −127.1 | −109.6 |
| ΔECoul | −7847.3 | −7807.0 | −7795.3 | 40.3 | 11.7 | 52.0 [12%] | |
| ΔEOrb | −6241.3 | −6018.8 | −5872.7 | 222.6 | 146.0 | 368.6 [88%] | |
| ΔΔEInt | 280.4 | 30.6 | 311.0 (85%) | ||||
| ΔΔEPrep | 97.4 | −43.3 | 54.1 (15%) | ||||
| Δ(ΔEInt + ΔEPrep) | 377.8 | −12.6 | 365.2 | ||||
| SiF4 | ΔEPauli | 957.8 | 961.9 | 831.5 | 4.1 | −130.4 | −126.3 |
| ΔECoul | −10558.3 | −10406.3 | −10370.2 | 152.0 | 36.1 | 188.2 [66%] | |
| ΔEOrb | −4277.9 | −4317.1 | −4182.5 | −39.2 | 134.7 | 95.5 [34%] | |
| ΔΔEInt | 117.0 | 40.4 | 157.3 (62%) | ||||
| ΔΔEPrep | 154.8 | −59.5 | 95.3 (38%) | ||||
| Δ(ΔEInt + ΔEPrep) | 271.7 | −19.1 | 252.6 | ||||