Table 16. Deviations of Exothermicities and Barrier Heights in Comparison to MP2/G3Large Single Point Calculations at B3LYP/6-31+G(d,p) Relaxed Geometries for 37 Elementary Steps in the Hydrolysis of MMP and DMPa.
| method | MP2 | B3LYP | PBEb | PM6 | PDDG | MIO | 3OB | 3OB/OPhyd | 3OB | 3OB/OPhyd | MP2 | MP2 |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| at geometry optimized by | B3LYP | B3LYP | B3LYP | B3LYP | B3LYP | B3LYP | B3LYP | B3LYP | 3OB | 3OB/OPhyd | 3OB | 3OB/OPhyd |
| com1 → ts1 (MMP,B) | 31.0 | –1.7 | –6.1 | –14.5 | +12.3 | –7.2 | +11.4 | –0.8 | –0.8 | +0.5 | ||
| com1 → int1 (MMP,E) | 30.6 | –1.4 | –5.7 | –16.4 | +14.8 | –7.0 | +12.9 | –0.8 | –1.5 | +0.6 | ||
| com1 → ts1_2 (MMP,B) | 41.5 | –2.1 | –7.4 | –11.9 | +9.4 | –3.3 | +9.7 | +1.1 | +9.8 | +1.8 | +1.8 | +1.1 |
| com1 → int1_2 (MMP,E) | 31.0 | –1.1 | –5.1 | –17.8 | +15.6 | –5.9 | +15.4 | +0.5 | +14.5 | –0.2 | +0.8 | +0.7 |
| int1_2 → ts2_0 (MMP,B) | 11.9 | –2.0 | –3.3 | +7.4 | –7.2 | +2.7 | –4.9 | +1.6 | –4.9 | +0.3 | –2.1 | +3.0 |
| int1_2 → ts2 (MMP,B) | 3.6 | +0.1 | –0.4 | +4.3 | +0.4 | –1.1 | –2.7 | –0.2 | +2.3 | +2.3 | +6.6 | +6.4 |
| int1_2 → com2 (MMP,E) | –28.8 | –0.9 | +3.4 | +20.4 | –17.6 | +4.4 | –16.6 | –1.8 | –15.7 | –0.9 | –1.8 | –1.8 |
| com1 → diss_tsa (MMP,B) | 36.8 | –4.2 | –10.2 | –6.2 | +11.8 | +4.9 | –2.8 | –2.2 | –7.8 | –6.0 | –2.0 | +0.4 |
| com1 → diss_int (MMP,E) | 19.6 | –6.5 | –7.5 | –4.6 | –14.8 | +0.3 | –23.1 | –10.5 | –22.5 | –10.0 | –1.0 | –1.4 |
| com1_w2 → ts1_2_w2 (MMP,B) | 39.9 | –2.1 | –8.5 | –24.0 | +10.0 | –12.7 | +5.3 | –4.8 | +6.2 | –3.1 | –1.5 | +1.9 |
| com1_w2 → int1_2a_w2 (MMP,E) | 28.0 | –0.5 | –4.4 | –21.6 | +16.4 | –7.9 | +12.8 | –2.1 | +11.9 | –2.8 | +0.2 | –0.1 |
| int1_2a_w2 → int1_2_w2 (MMP,E) | 0.4 | +0.8 | +0.5 | +4.0 | +1.3 | +2.5 | +2.9 | +3.0 | +2.7 | +2.7 | +1.1 | +1.1 |
| int1_2_w2 → ts2_0_w2 (MMP,B) | 11.4 | –1.8 | –3.7 | +1.4 | –0.2 | –5.4 | –9.0 | –3.5 | –7.7 | –2.1 | –4.2 | +0.0 |
| com1_da → ts1_da (MMP,B) | 55.0 | –3.1 | –6.8 | –7.7 | –11.1 | –0.2 | +2.0 | –0.7 | +4.2 | –0.3 | +7.4 | +1.0 |
| com1_da → int_da (MMP,E) | 4.5 | –2.0 | –1.8 | +1.4 | +4.0 | –2.0 | –1.9 | –1.9 | –1.7 | –1.6 | –0.2 | –0.4 |
| com1 → ts1 (DMP,B) | 38.6 | –1.4 | –5.9 | –15.0 | +5.8 | –7.3 | +9.4 | –0.5 | +9.9 | –0.9 | +0.6 | +0.5 |
| com1 → int1 (DMP,E) | 35.4 | –0.2 | –4.4 | –19.4 | +11.8 | –7.6 | +13.8 | –0.9 | +12.9 | –1.6 | +1.8 | +1.4 |
| int1 → int1_2 (DMP,E) | 1.3 | –0.7 | –1.3 | +1.9 | +1.6 | +1.3 | +1.3 | +2.1 | +0.7 | +0.8 | +0.1 | +0.3 |
| int1_2 → ts2 (DMP,B) | 0.6 | –0.5 | –0.5 | +3.1 | –2.4 | +1.2 | –0.8 | +1.5 | –0.4 | +3.4 | –0.1 | –0.4 |
| int1_2 → com2 (DMP,E) | –35.2 | –0.7 | +4.3 | +21.2 | –15.2 | +6.0 | –15.0 | –1.0 | –13.5 | +1.0 | –1.8 | –1.7 |
| n_com1 → n_ts3 (DMP,B) | 33.6 | –1.4 | –8.1 | –11.0 | +28.5 | +0.2 | +16.5 | +4.4 | +12.2 | +0.8 | +2.3 | +1.2 |
| n_com1 → n_int1 (DMP,E) | 13.2 | +0.4 | –3.2 | –15.6 | +21.8 | –4.9 | +18.2 | +3.6 | +17.7 | +3.1 | +0.8 | +1.1 |
| n_int1 → n_ts4 (DMP,B) | 22.9 | –1.6 | –5.4 | +8.0 | +13.4 | +5.1 | +0.6 | +1.2 | –3.6 | –1.4 | +0.2 | +0.8 |
| n_int1 → n_com2 (DMP,E) | –15.8 | –1.9 | +0.9 | +23.2 | –14.9 | +3.7 | –18.7 | –4.2 | –18.9 | –4.2 | –0.6 | –1.0 |
| DMP_P → diss_ts (DMP,B) | 40.9 | –2.9 | –9.1 | –2.3 | +11.2 | +8.8 | +0.2 | –0.7 | –2.2 | –3.2 | –0.6 | –1.5 |
| DMP_P → diss_prod (DMP,E) | 28.2 | –3.8 | –6.7 | –12.6 | –0.9 | –0.9 | –6.1 | –5.2 | –18.7 | –7.3 | +5.6 | +4.0 |
| diss_prod2 → diss_ts2 (DMP,B) | 13.5 | +0.7 | –2.5 | +12.1 | +18.3 | +10.4 | +8.9 | +5.1 | +16.9 | +4.7 | –2.8 | –1.2 |
| diss_prod2 → MMP_P (DMP,E) | –29.8 | +3.6 | +6.7 | +18.4 | +12.3 | +0.6 | +8.1 | +5.1 | +19.6 | +8.1 | –2.2 | –1.2 |
| diss_w_reac → diss_w_ts (DMP,B) | 20.9 | –2.3 | –7.4 | –8.0 | +10.8 | +0.7 | +1.3 | +0.7 | +2.1 | +1.5 | +1.0 | +0.8 |
| diss_w_reac → diss_w_prod (DMP,E) | 18.4 | –2.6 | –5.6 | –6.5 | +1.0 | +0.3 | –2.5 | –2.9 | –12.9 | –2.9 | +12.0 | +0.0 |
| diss_w_prod2 → diss_w_ts2 (DMP,B) | 1.9 | +0.2 | –1.6 | +0.9 | +10.9 | +0.3 | +3.3 | +2.8 | +16.6 | +3.4 | –8.2 | –0.1 |
| diss_w_prod2 → diss_w_reac2 (DMP,E) | –21.0 | +2.8 | +6.2 | +14.5 | +7.7 | –0.7 | +2.2 | +2.3 | +14.7 | +2.0 | –8.3 | +0.1 |
| n_w_com1 → n_w_ts3 (DMP,B) | 28.2 | –1.8 | –10.1 | –24.3 | +32.4 | –8.9 | +13.7 | +0.2 | +10.6 | –0.2 | –0.2 | +0.2 |
| n_w_com1 → n_w_int1 (DMP,E) | 13.1 | +1.0 | –3.1 | –15.7 | +22.2 | –5.8 | +17.5 | +2.8 | +17.3 | +2.7 | +0.6 | +0.7 |
| n_w_int1 → n_w_int2 (DMP,E) | –0.5 | +0.5 | +0.4 | –0.0 | +0.8 | +0.6 | +1.0 | +1.0 | +0.6 | +0.6 | +0.4 | +0.4 |
| n_w_int2 → n_w_ts4 (DMP,B) | 15.1 | –2.3 | –6.2 | –2.6 | +17.2 | –3.1 | –2.9 | –2.7 | –0.9 | –1.1 | +4.2 | +2.1 |
| n_w_int2 → n_w_com2 (DMP,E) | –13.0 | –2.0 | +1.3 | +23.8 | –14.8 | +4.1 | –19.0 | –4.4 | ||||
| MAD | 1.8 | 4.7 | 11.5 | 11.4 | 4.1 | 8.5 | 2.5 | 9.8 | 2.5 | 2.5 | 1.1 | |
| MAX | 6.5 | 10.3 | 24.3 | 32.4 | 12.7 | 23.1 | 10.5 | 22.5 | 10.0 | 12.0 | 6.4 |
a
Compilation from ref (43); no zero-point corrections are included in either exothermicity or barrier heights. All quantities are given in kcal/mol. The processes are labeled in the notation of ref (43); “E” stands for “Exothermicity,” “B” for “Barrier;” coordinates are listed in the Supporting Information.
b
Basis set is 6-31+G(d,p).